Composition containing refrigerant, and refrigeration method using said composition, operating method for refrigeration device, and refrigeration device

ABSTRACT

The present disclosure provides a composition comprising a refrigerant characterized by having a coefficient of performance (COP) and a refrigerating capacity equivalent to or higher than those of R404A, and having a sufficiently low GWP. Specifically, the present disclosure provides a composition comprising a refrigerant, the refrigerant comprising trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), wherein HFO-1132 (E) is present in an amount of 35.0 to 65.0 mass %, and HFO-1234yf is present in an amount of 65.0 to 35.0 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf, and wherein the refrigerant is for use in operating a refrigeration cycle in which the evaporation temperature is −75 to −5° C.

TECHNICAL FIELD

The present disclosure relates to a composition comprising a refrigerantand a refrigeration method, a method for operating a refrigerationapparatus, and a refrigeration apparatus, all of which use thecomposition.

BACKGROUND ART

Amid worldwide discussion about global warming as a highly seriousissue, the development of environmentally friendly air conditioners,refrigeration apparatus, etc. has become increasingly important.

Various mixed refrigerants that have a low global warming potential(GWP) and that can replace R404A, which is used as a refrigerant for airconditioners, such as home air conditioners, have currently beenproposed. For example, Patent Literature (PTL) 1 and PTL 2 disclose, asan alternative refrigerant for R404A, a refrigerant compositioncomprising difluoromethane (R32), pentafluoroethane (R125),2,3,3,3-tetrafluoropropene (R1234yf), and 1,1,1,2-tetrafluoroethane(R134a).

Additionally, various mixed refrigerants that have a low GWP and thatcan replace 1,1,1,2-tetrafluoroethane (HFC-134a or R134a), which is usedas a refrigerant for air conditioners, such as home air conditioners,have been proposed (e.g., PTL 3).

CITATION LIST Patent Literature

-   PTL 1: WO 2010/059677-   PTL 2: WO 2011/163117-   PTL 3: WO 2005/105947

SUMMARY OF INVENTION Technical Problem

An object of the present disclosure is to provide a compositioncomprising a refrigerant characterized by having a coefficient ofperformance (COP) and a refrigerating capacity (which may be expressedas “cooling capacity” or “capacity”) equivalent to or higher than thoseof R404A, and having a sufficiently low GWP. Another object of thepresent disclosure is to provide a composition comprising a refrigerantcharacterized by having a coefficient of performance (COP) and arefrigerating capacity (which may be expressed as “cooling capacity” or“capacity”) equivalent to or higher than those of R134a, and having asufficiently low GWP. Still another object of the present disclosure isto provide a refrigeration method, a method for operating arefrigeration apparatus, and a refrigeration apparatus, all of which usethe above composition.

Solution to Problem

The present disclosure provides the invention according to the followingembodiments.

Item 1.

A composition comprising a refrigerant,

the refrigerant comprising trans-1,2-difluoroethylene (HFO-1132 (E)) and2,3,3,3-tetrafluoropropene (HFO-1234yf),

wherein HFO-1132 (E) is present in an amount of 35.0 to 65.0 mass %, andHFO-1234yf is present in an amount of 65.0 to 35.0 mass %, based on thetotal mass of HFO-1132 (E) and HFO-1234yf, and

wherein the refrigerant is for use in operating a refrigeration cycle inwhich the evaporation temperature is −75 to −5° C.

Item 2.

The composition according to Item 1, wherein HFO-1132 (E) is present inan amount of 41.3 to 53.5 mass %, and HFO-1234yf is present in an amountof 58.7 to 46.5 mass %, based on the total mass of HFO-1132 (E) andHFO-1234yf.

Item 3.

The composition according to Item 1 or 2, wherein the refrigerantconsists of HFO-1132 (E) and HFO-1234yf.

Item 4.

A composition comprising a refrigerant,

the refrigerant comprising trans-1,2-difluoroethylene (HFO-1132 (E)) and2,3,3,3-tetrafluoropropene (HFO-1234yf),

wherein HFO-1132 (E) is present in an amount of 40.5 to 49.2 mass %, andHFO-1234yf is present in an amount of 59.5 to 50.8 mass %, based on thetotal mass of HFO-1132 (E) and HFO-1234yf.

Item 5.

The composition according to Item 4, wherein the refrigerant consists ofHFO-1132 (E) and HFO-1234yf.

Item 6.

The composition according to Item 4 or 5, wherein the refrigerant is foruse in operating a refrigeration cycle in which the evaporationtemperature is −75 to 15° C.

Item 7.

The composition according to any one of Items 1 to 6, which is for useas an alternative refrigerant for R12, R22, R134a, R404A, R407A, R407C,R407F, R407H, R410A, R413A, R417A, R422A, R422B, R422C, R422D, R423A,R424A, R426A, R427A, R430A, R434A, R437A, R438A, R448A, R449A, R449B,R449C, R452A, R452B, R454A, R454B, R454C, R455A, R465A, R502, R507, orR513A.

Item 8.

A composition comprising a refrigerant,

the refrigerant comprising trans-1,2-difluoroethylene (HFO-1132 (E)) and2,3,3,3-tetrafluoropropene (HFO-1234yf),

wherein HFO-1132 (E) is present in an amount of 31.1 to 39.8 mass %, andHFO-1234yf is present in an amount of 68.9 to 60.2 mass %, based on thetotal mass of HFO-1132 (E) and HFO-1234yf.

Item 9.

The composition according to Item 8, wherein HFO-1132 (E) is present inan amount of 31.1 to 37.9 mass %, and HFO-1234yf is present in an amountof 68.9 to 62.1 mass %, based on the total mass of HFO-1132 (E) andHFO-1234yf.

Item 10.

The composition according to Item 8 or 9, wherein the refrigerantconsists of HFO-1132 (E) and HFO-1234yf.

Item 11.

The composition according to any one of Items 8 to 10, wherein therefrigerant is for use in operating a refrigeration cycle in which theevaporation temperature is −75 to 15° C.

Item 12.

The composition according to any one of Items 8 to 11, which is for useas an alternative refrigerant for R134a, R1234yf, or CO₂ (R744).

Item 13.

A composition comprising a refrigerant,

the refrigerant comprising trans-1,2-difluoroethylene (HFO-1132 (E)) and2,3,3,3-tetrafluoropropene (HFO-1234yf),

wherein HFO-1132 (E) is present in an amount of 21.0 to 28.4 mass %, andHFO-1234yf is present in an amount of 79.0 to 71.6 mass %, based on thetotal mass of HFO-1132 (E) and HFO-1234yf.

Item 14.

The composition according to Item 13, wherein the refrigerant consistsof HFO-1132 (E) and HFO-1234yf.

Item 15.

The composition according to Item 13 or 14, which is for use as analternative refrigerant for R12, R22, R134a, R404A, R407A, R407C, R407F,R407H, R410A, R413A, R417A, R422A, R422B, R422C, R422D, R423A, R424A,R426A, R427A, R430A, R434A, R437A, R438A, R448A, R449A, R449B, R449C,R452A, R452B, R454A, R454B, R454C, R455A, R465A, R502, R507, R513A,R1234yf, or R1234ze.

Item 16.

A composition comprising a refrigerant,

the refrigerant comprising trans-1,2-difluoroethylene (HFO-1132 (E)) and2,3,3,3-tetrafluoropropene (HFO-1234yf),

wherein HFO-1132 (E) is present in an amount of 12.1 to 72.0 mass %, andHFO-1234yf is present in an amount of 87.9 to 28.0 mass %, based on thetotal mass of HFO-1132 (E) and HFO-1234yf, and

wherein the refrigerant is for use in an air-conditioning system forvehicles.

Item 17.

The composition according to Item 16, wherein the air-conditioningsystem is for gasoline vehicles, hybrid vehicles, electric vehicles, orhydrogen vehicles.

Item 18.

The composition according to Item 16 or 17, wherein the refrigerantconsists of HFO-1132 (E) and HFO-1234yf.

Item 19.

The composition according to any one of Items 16 to 18, which is for useas an alternative refrigerant for R12, R134a, or R1234yf.

Item 20.

The composition according to any one of Items 1 to 19, comprising atleast one substance selected from the group consisting of water,tracers, ultraviolet fluorescent dyes, stabilizers, and polymerizationinhibitors.

Item 21.

The composition according to any one of Items 1 to 20, the compositionfurther comprising a refrigerant oil and being for use as a workingfluid for a refrigeration apparatus.

Item 22.

The composition according to Item 21, wherein the refrigerant oilcontains at least one polymer selected from the group consisting ofpolyalkylene glycol (PAG), polyol ester (POE), and polyvinyl ether(PVE).

Item 23.

A refrigeration method comprising operating a refrigeration cycle usingthe composition of any one of Items 1 to 22.

Item 24.

A refrigeration method comprising operating a refrigeration cycle inwhich the evaporation temperature is −75 to −5° C., using a compositioncomprising a refrigerant, the refrigerant comprisingtrans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene(HFO-1234yf),

wherein HFO-1132 (E) is present in an amount of 35.0 to 65.0 mass %, andHFO-1234yf is present in an amount of 65.0 to 35.0 mass %, based on thetotal mass of HFO-1132 (E) and HFO-1234yf.

Item 25.

The refrigeration method according to Item 24, wherein HFO-1132 (E) ispresent in an amount of 41.3 to 53.5 mass %, and HFO-1234yf is presentin an amount of 58.7 to 46.5 mass %, based on the total mass of HFO-1132(E) and HFO-1234yf.

Item 26.

The refrigeration method according to Item 24 or 25, wherein therefrigerant consists of HFO-1132 (E) and HFO-1234yf.

Item 27.

A refrigeration method comprising operating a refrigeration cycle usinga composition comprising a refrigerant, the refrigerant comprisingtrans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene(HFO-1234yf),

wherein HFO-1132 (E) is present in an amount of 40.5 to 49.2 mass %, andHFO-1234yf is present in an amount of 59.5 to 50.8 mass %, based on thetotal mass of HFO-1132 (E) and HFO-1234yf.

Item 28.

The refrigeration method according to Item 27, wherein the refrigerantconsists of HFO-1132 (E) and HFO-1234yf.

Item 29.

The refrigeration method according to Item 27 or 28, wherein therefrigerant has an evaporation temperature of −75 to 15° C. in therefrigeration cycle.

Item 30.

A refrigeration method comprising operating a refrigeration cycle usinga composition comprising a refrigerant, the refrigerant comprisingtrans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene(HFO-1234yf),

wherein HFO-1132 (E) is present in an amount of 31.1 to 39.8 mass %, andHFO-1234yf is present in an amount of 68.9 to 60.2 mass %, based on thetotal mass of HFO-1132 (E) and HFO-1234yf.

Item 31.

The refrigeration method according to Item 30, wherein HFO-1132 (E) ispresent in an amount of 31.1 to 37.9 mass %, and HFO-1234yf is presentin an amount of 68.9 to 62.1 mass %, based on the total mass of HFO-1132(E) and HFO-1234yf.

Item 32.

The refrigeration method according to Item 30 or 31, wherein therefrigerant consists of HFO-1132 (E) and HFO-1234yf.

Item 33.

The refrigeration method according to any one of Items 30 to 32, whereinthe refrigerant has an evaporation temperature of −75 to 15° C. in therefrigeration cycle.

Item 34.

A refrigeration method comprising operating a refrigeration cycle usinga composition comprising a refrigerant, the refrigerant comprisingtrans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene(HFO-1234yf),

wherein HFO-1132 (E) is present in an amount of 21.0 to 28.4 mass %, andHFO-1234yf is present in an amount of 79.0 to 71.6 mass %, based on thetotal mass of HFO-1132 (E) and HFO-1234yf.

Item 35.

The refrigeration method according to Item 34, wherein the refrigerantconsists of HFO-1132 (E) and HFO-1234yf.

Item 36.

A refrigeration method comprising operating a refrigeration cycle usinga composition comprising a refrigerant, the refrigerant comprisingtrans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene(HFO-1234yf),

wherein HFO-1132 (E) is present in an amount of 12.1 to 72.0 mass %, andHFO-1234yf is present in an amount of 87.9 to 28.0 mass %, based on thetotal mass of HFO-1132 (E) and HFO-1234yf, and wherein the refrigerantis for use in an air-conditioning system for vehicles.

Item 37.

The refrigeration method according to Item 36, wherein theair-conditioning system is for gasoline vehicles, hybrid vehicles,electric vehicles, or hydrogen vehicles.

Item 38.

The refrigeration method according to Item 36 or 37, wherein therefrigerant consists of HFO-1132 (E) and HFO-1234yf.

Item 39.

A method for operating a refrigeration apparatus that operates arefrigeration cycle using the composition of any one of Items 1 to 22.

Item 40.

A refrigeration apparatus comprising the composition of any one of Items1 to 22 as a working fluid.

Item 41.

The refrigeration apparatus according to Item 40, which is anair-conditioning system, a refrigerator, a freezer, a water cooler, anice maker, a refrigerated showcase, a freezing showcase, a freezing andrefrigerating unit, a refrigerating machine for freezing andrefrigerating warehouses, an air-conditioning system for vehicles, aturbo refrigerating machine, or a screw refrigerating machine.

Item 42.

The composition according to any one of Items 1 to 22, which is for useas a refrigerant.

Item 43.

The composition according to Item 42, which is for use as a refrigerantin a refrigeration apparatus.

Item 44.

The composition according to Item 43, wherein the refrigerationapparatus is an air-conditioning system, a refrigerator, a freezer, awater cooler, an ice maker, a refrigerated showcase, a freezingshowcase, a freezing and refrigerating unit, a refrigerating machine forfreezing and refrigerating warehouses, an air-conditioning system forvehicles, a turbo refrigerating machine, or a screw refrigeratingmachine.

Item 45.

Use of the composition of any one of Items 1 to 22 as a refrigerant.

Item 46.

The use according to Item 45 in a refrigeration apparatus.

Item 47.

The use according to Item 46, wherein the refrigeration apparatus is anair-conditioning system, a refrigerator, a freezer, a water cooler, anice maker, a refrigerated showcase, a freezing showcase, a freezing andrefrigerating unit, a refrigerating machine for freezing andrefrigerating warehouses, an air-conditioning system for vehicles, aturbo refrigerating machine, or a screw refrigerating machine.

Advantageous Effects of Invention

The composition comprising a refrigerant according to the presentdisclosure is characterized by having a coefficient of performance (COP)and a refrigerating capacity equivalent to or higher than those ofR404A, and having a sufficiently low GWP. Additionally, the compositioncomprising a refrigerant according to the present disclosure ischaracterized by having a coefficient of performance (COP) and arefrigerating capacity equivalent to or higher than those of R134a, andhaving a sufficiently low GWP.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a diagram illustrating an experimental apparatus for examiningflammability (flammable or non-flammable).

DESCRIPTION OF EMBODIMENTS

To solve the above problems, the present inventors conducted extensiveresearch and found that a composition comprising a mixed refrigerantcomprising trans-1,2-difluoroethylene (HFO-1132 (E)) and2,3,3,3-tetrafluoropropene (HFO-1234yf) has the above characteristics.

The present disclosure has been completed as a result of furtherresearch based on the above findings. The present invention encompassesthe following embodiments.

DEFINITION OF TERMS

The numerical range expressed by using “to” in the present specificationindicates a range that includes numerical values before and after “to”stated as the minimum and maximum values respectively.

In the present specification, the terms “comprise” and “contain”includes the concepts of “consisting essentially of” and “consistingof.”

In the present specification, the term “refrigerant” includes at leastcompounds that are specified in ISO817 (International Organization forStandardization), and that are given a refrigerant number (ASHRAEnumber) representing the type of refrigerant with “R” at the beginning;and further includes refrigerants that have characteristics equivalentto those of such refrigerants even if a refrigerant number is not yetgiven.

Refrigerants are broadly divided into fluorocarbon-based compounds andnon-fluorocarbon-based compounds in terms of the structure of thecompounds. Fluorocarbon-based compounds include chlorofluorocarbons(CFC), hydrochlorofluorocarbons (HCFC), and hydrofluorocarbons (HFC).Non-fluorocarbon-based compounds include propane (R290), propylene(R1270), butane (R600), isobutane (R600a), carbon dioxide (R744),ammonia (R717), and the like.

The term “composition comprising a refrigerant” used in the presentspecification at least includes:

(1) a refrigerant itself (including a mixture of refrigerants, i.e., amixed refrigerant);

(2) a composition that can be used for obtaining a working fluid for arefrigeration apparatus by further comprising one or more othercomponents and mixing with at least a refrigerant oil; and

(3) a working fluid for a refrigeration apparatus, containing arefrigerant oil.

Among these three modes, composition (2) is referred to as a“refrigerant composition” in the present specification to distinguish itfrom a refrigerant itself (including a mixed refrigerant). Further, theworking fluid for a refrigeration apparatus (3) is referred to as “arefrigerant oil-containing working fluid” to distinguish it from the“refrigerant composition.”

In the present specification, when the term “alternative” is used in acontext in which the first refrigerant is replaced with the secondrefrigerant, the first type of alternative means that equipment designedfor operation using the first refrigerant can be operated using thesecond refrigerant under optimum conditions, optionally with changes ofonly a few parts (at least one of the following: refrigerant oil,gasket, packing, expansion valve, dryer, other parts) and equipmentadjustment. In other words, this type of alternative means that the sameequipment is operated with an alternative refrigerant. Embodiments ofthis type of alternative include drop-in alternatives, nearly drop-inalternatives, and retrofits, in the order in which the extent of changesand adjustment necessary for replacing the first refrigerant with thesecond refrigerant is smaller.

The term “alternative” also includes a second type of alternative, whichmeans that equipment designed for operation using the second refrigerantis operated for the same use as the existing use with the firstrefrigerant by using the second refrigerant. This type of alternativemeans that the same use is achieved with an alternative refrigerant.

In the present specification, the term “refrigeration apparatus” in thebroad sense refers to apparatuses in general that draw heat from anobject or space to make its temperature lower than the temperature ofthe ambient air, and maintain the low temperature. In other words,refrigeration apparatuses in the broad sense refer to conversionapparatuses that gain energy from the outside to do work, and thatperform energy conversion, in order to transfer heat from where thetemperature is lower to where the temperature is higher. In the presentdisclosure, “refrigeration apparatus” is synonymous with “heat pump” inthe broad sense.

In the present disclosure, the term “refrigeration apparatus” isdistinguished from “heat pump” in the narrow sense, depending on thedifference in the applied temperature range and operating temperature.In this case, an apparatus whose low-temperature heat source is placedin a temperature range lower than the air temperature may be called a“refrigeration apparatus,” while an apparatus whose low-temperature heatsource is placed near the air temperature to use the heat-release actioncaused by driving the refrigeration cycle may be called a “heat pump.”Additionally, there are apparatuses that have both the function ofrefrigeration apparatuses in the narrow sense and the function of heatpumps in the narrow sense, despite them being a single machine, such asair conditioners that provide both a cooling mode and a heating mode. Inthe present specification, unless otherwise indicated, the terms“refrigeration apparatus” and “heat pump” are used in the broad sensethroughout the specification.

In the present specification, the term “temperature glide” can berephrased as an absolute value of the difference between the startingtemperature and the ending temperature of the phase change process ofthe composition comprising a refrigerant according to the presentdisclosure within the constituent elements of a heat cycle system.

In the present specification, the term “air-conditioning system forvehicles” is a type of refrigeration apparatus for use in vehicles, suchas gasoline vehicles, hybrid vehicles, electric vehicles, and hydrogenvehicles. The air-conditioning system for vehicles refers to arefrigeration apparatus that has a refrigeration cycle in which heatexchange is performed by an evaporator using a liquid refrigerant, theevaporated refrigerant gas is absorbed by a compressor, theadiabatically compressed refrigerant gas is cooled and liquefied with acondenser, the liquefied refrigerant is adiabatically expanded bypassing it through an expansion valve, and then the refrigerant issupplied again in the form of a liquid to the evaporator.

In the present specification, the term “turbo refrigerating machine” isa type of large chiller refrigeration apparatus and refers to arefrigeration apparatus that has a refrigeration cycle in which heatexchange is performed by an evaporator using a liquid refrigerant, theevaporated refrigerant gas is absorbed by a centrifugal compressor, theadiabatically compressed refrigerant gas is cooled and liquefied with acondenser, the liquefied refrigerant is adiabatically expanded bypassing it through an expansion valve, and then the refrigerant issupplied again in the form of a liquid to the evaporator. The term“large chiller refrigerating machine” is a type of chiller and refers toa large air-conditioner that is intended for air conditioning in a unitof a building.

In the present specification, the term “saturation pressure” refers to apressure of saturated vapor. In the present specification, the term“saturation temperature” refers to a temperature of saturated vapor.

In the present specification, the phrase “evaporation temperature in arefrigeration cycle” refers to a temperature at which a refrigerantliquid absorbs heat and becomes vapor in the evaporation step of therefrigeration cycle. The evaporation temperature in a refrigerationcycle can be determined by measuring the temperature of the evaporatorinlet and/or the evaporator outlet. The evaporation temperature of asimple refrigerant or azeotropic refrigerant is constant. However, theevaporation temperature of a non-azeotropic refrigerant is an averagevalue of the temperature at the evaporator inlet and the dew pointtemperature. More specifically, the evaporation temperature of anon-azeotropic refrigerant can be calculated with the followingequation.Evaporation temperature=(evaporator inlet temperature+dew pointtemperature)/2.

In the present specification, the term “discharge temperature” refers toa temperature of the mixed refrigerant at the outlet of a compressor.

In the present specification, the term “evaporation pressure” refers toa saturation pressure at an evaporation temperature. In the presentspecification, the term “condensation pressure” refers to a saturationpressure at a condensation temperature.

In the present specification, the term “critical temperature” refers toa temperature at the critical point, and a temperature boundary; i.e.,unless the temperature is equivalent to or lower than the criticaltemperature, gas would not be converted into a liquid by compressing thegas.

In the present specification, “non-flammable” refrigerants refer tothose whose worst case formulation for flammability (WCF), which is themost flammable point in the allowable refrigerant concentration rangeaccording to the US ANSI/ASHRAE Standard 34-2013, is classified as Class1.

In the present specification, “slightly flammable” refrigerants refersto those whose WCF formulation is classified as Class 2L according toANSI/ASHRAE Standard 34-2013

In the present specification, “weakly flammable” refrigerants refers tothose whose WCF formulation is classified as Class 2 according toANSI/ASHRAE Standard 34-2013.

In the present specification, the GWP (AR4) is evaluated based on thevalues stated in the Intergovernmental Panel on Climate Change (IPCC)fourth report.

1. Composition

The composition according to the present disclosure comprises arefrigerant. Examples of the refrigerant include Refrigerant 1,Refrigerant 2, Refrigerant 3, Refrigerant 4, and Refrigerant 5.Refrigerant 1, Refrigerant 2, Refrigerant 3, Refrigerant 4, andRefrigerant 5 are described below. In the present specification, “therefrigerant according to the present disclosure” refers to Refrigerant1, Refrigerant 2, Refrigerant 3, Refrigerant 4, or Refrigerant 5.

1.1 Refrigerant 1

In an embodiment, the refrigerant contained in the composition accordingto the present disclosure comprises HFO-1132 (E) and HFO-1234yf, whereinHFO-1132 (E) is present in an amount of 35.0 to 65.0 mass %, andHFO-1234yf is present in an amount of 65.0 to 35.0 mass %, based on thetotal mass of HFO-1132 (E) and HFO-1234yf. This refrigerant may bereferred to as “Refrigerant 1.”

In the present disclosure, Refrigerant 1 is for use in operating arefrigeration cycle in which the evaporation temperature is −75 to −5°C.

Refrigerant 1 has the above feature and thus has the followingcharacteristics: (1) the GWP is sufficiently low (100 or less); (2) ithas a COP equivalent to or higher than that of R404A; and (3) it has arefrigerating capacity equivalent to or higher than that of R404A.

Since Refrigerant 1 comprises HFO-1132 (E) in an amount of 35.0 mass %or more based on the total mass of HFO-1132 (E) and HFO-1234yf,Refrigerant 1 has a refrigerating capacity equivalent to or higher thanthat of R404A. Moreover, since Refrigerant 1 comprises HFO-1132 (E) inan amount of 65.0 mass % or less based on the total mass of HFO-1132 (E)and HFO-1234yf, the saturation pressure of Refrigerant 1 at a saturationtemperature of 40° C. in the refrigeration cycle can be maintainedwithin a suitable range (in particular 2.10 Mpa or less).

Refrigerant 1 may have a refrigerating capacity of 95% or more,preferably 98% or more, more preferably 100% or more, even morepreferably 101% or more, and particularly preferably 102% or more,relative to that of R404A.

Since the GWP is 100 or less, Refrigerant 1 can notably reduce theburden on the environment from a global warming perspective, comparedwith other general-purpose refrigerants.

In Refrigerant 1, the ratio of refrigerating capacity to power consumedin a refrigeration cycle (coefficient of performance (COP)) relative tothat of R404A is preferably high, from the viewpoint of energyconsumption efficiency. Specifically, the COP relative to that of R404Ais preferably 98% or more, more preferably 100% or more, andparticularly preferably 102% or more.

In Refrigerant 1, it is preferred that HFO-1132 (E) be present in anamount of 40.5 to 59.0 mass %, and HFO-1234yf be present in an amount of59.5 to 41.0 mass %, based on the total mass of HFO-1132 (E) andHFO-1234yf. In this case, Refrigerant 1 has a GWP of 100 or less, a COPof 101% or more relative to that of R404A, and a refrigerating capacityof 99% or more relative to that of R404A. Further, in this case,Refrigerant 1 has a saturation pressure of 1.75 MPa or more and 2.00 MPaor less at a saturation temperature of 40° C., and is thus applicable tocommercially available refrigeration apparatuses for R404A withoutsignificant design change.

In Refrigerant 1, it is more preferred that HFO-1132 (E) be present inan amount of 41.3 to 59.0 mass %, and HFO-1234yf be present in an amountof 58.7 to 41.0 mass %, based on the total mass of HFO-1132 (E) andHFO-1234yf. In this case, Refrigerant 1 has a GWP of 100 or less, a COPof 101% or more relative to that of R404A, and a refrigerating capacityof 99.5% or more relative to that of R404A. Further, in this case,Refrigerant 1 has a saturation pressure of 1.76 MPa or more and 2.00 MPaor less at a saturation temperature of 40° C., and is thus applicable tocommercially available refrigeration apparatuses for R404A withoutsignificant design change.

In Refrigerant 1, it is further preferred that HFO-1132 (E) be presentin an amount of 41.3 to 55.0 mass %, and HFO-1234yf be present in anamount of 58.7 to 45.0 mass %, based on the total mass of HFO-1132 (E)and HFO-1234yf. In this case, Refrigerant 1 has a GWP of 100 or less, aCOP of 101% or more relative to that of R404A, and a refrigeratingcapacity of 99.5% or more relative to that of R404A. Further, in thiscase, Refrigerant 1 has a saturation pressure of 1.76 MPa or more and1.95 MPa or less at a saturation temperature of 40° C., and is thusapplicable to commercially available refrigeration apparatuses for R404Awithout significant design change.

In Refrigerant 1, it is particularly preferred that HFO-1132 (E) bepresent in an amount of 41.3 to 53.5 mass %, and HFO-1234yf be presentin an amount of 58.7 to 46.5 mass %, based on the total mass of HFO-1132(E) and HFO-1234yf. In this case, Refrigerant 1 has characteristics ofhaving a GWP of 100 or less, a COP of 102% or more relative to that ofR404A, and a refrigerating capacity of 99.5% or more relative to that ofR404A, as well as being slightly flammable according to ASHRAE Standards(Class 2L). Further, in this case, Refrigerant 1 has a saturationpressure of 1.76 MPa or more and 1.94 MPa or less at a saturationtemperature of 40° C., and is thus applicable to commercially availablerefrigeration apparatuses for R404A without significant design change.

In Refrigerant 1, it is particularly preferred that HFO-1132 (E) bepresent in an amount of 41.3 to 51.0 mass %, and HFO-1234yf be presentin an amount of 58.7 to 49.0 mass %, based on the total mass of HFO-1132(E) and HFO-1234yf. In this case, Refrigerant 1 has characteristics ofhaving a GWP of 100 or less, a COP of 102% or more relative to that ofR404A, and a refrigerating capacity of 99% or more relative to that ofR404A, as well as being slightly flammable according to ASHRAE Standards(Class 2L). Further, in this case, Refrigerant 1 has a saturationpressure of 1.76 MPa or more and 1.90 MPa or less at a saturationtemperature of 40° C., and is thus applicable to commercially availablerefrigeration apparatuses for R404A without significant design change.

In Refrigerant 1, it is most preferred that HFO-1132 (E) be present inan amount of 41.3 to 49.2 mass %, and HFO-1234yf be present in an amountof 58.7 to 50.8 mass %, based on the total mass of HFO-1132 (E) andHFO-1234yf. In this case, Refrigerant 1 has characteristics of having aGWP of 100 or less, a COP of 102% or more relative to that of R404A, anda refrigerating capacity of 99.5% or more relative to that of R404A, aswell as being slightly flammable according to ASHRAE Standards (Class2L). Further, in this case, Refrigerant 1 has a saturation pressure of1.76 MPa or more and 1.88 MPa or less at a saturation temperature of 40°C., and is thus applicable to commercially available refrigerationapparatuses for R404A without significant design change.

In Refrigerant 1, the saturation pressure at a saturation temperature of40° C. is usually 2.10 MPa or less, preferably 2.00 MPa or less, morepreferably 1.95 MPa or less, even more preferably 1.90 MPa or less, andparticularly preferably 1.88 MPa or less. If the saturation pressure ata saturation temperature of 40° C. is within the above range,Refrigerant 1 is applicable to commercially available refrigerationapparatuses for R404A without significant design change.

In Refrigerant 1, the saturation pressure at a saturation temperature of40° C. is usually 1.70 MPa or more, preferably 1.73 MPa or more, morepreferably 1.74 MPa or more, even more preferably 1.75 MPa or more, andparticularly preferably 1.76 MPa or more. If the saturation pressure ata saturation temperature of 40° C. is within the above range,Refrigerant 1 is applicable to commercially available refrigerationapparatuses for R404A without significant design change.

In the present disclosure, when Refrigerant 1 is used for operating arefrigeration cycle, the discharge temperature is preferably 150° C. orlower, more preferably 140° C. or lower, even more preferably 130° C. orlower, and particularly preferably 120° C. or lower, from the viewpointof extending the life of the components of a commercially availablerefrigeration apparatus for R404A.

The use of Refrigerant 1 for operating a refrigeration cycle in whichthe evaporation temperature is −75 to −5° C. is advantageous in terms ofensuring a refrigerating capacity equivalent to or higher than that ofR404A.

In a refrigeration cycle in which Refrigerant 1 according to the presentdisclosure is used, when the evaporation temperature exceeds −5° C., thecompression ratio becomes less than 2.5, which reduces the efficiency ofthe refrigeration cycle. In a refrigeration cycle in which Refrigerant 1according to the present disclosure is used, when the evaporationtemperature is less than −75° C., the evaporation pressure becomes lessthan 0.02 MPa, which makes suction of the refrigerant into a compressordifficult. The compression ratio is calculated with the followingequation.Compression ratio=condensation pressure(Mpa)/evaporation pressure(Mpa).

In a refrigeration cycle in which Refrigerant 1 according to the presentdisclosure is used, the evaporation temperature is preferably −7.5° C.or lower, more preferably −10° C. or lower, and even more preferably−35° C. or lower.

In a refrigeration cycle in which Refrigerant 1 according to the presentdisclosure is used, the evaporation temperature is preferably −65° C. ormore, more preferably −60° C. or more, even more preferably −55° C. ormore, and particularly preferably −50° C. or more.

In a refrigeration cycle in which Refrigerant 1 according to the presentdisclosure is used, the evaporation temperature is preferably −65° C. ormore and −5° C. or lower, more preferably −60° C. or more and −5° C. orlower, even more preferably −55° C. or more and −7.5° C. or lower, andparticularly preferably-50° C. or more and −10° C. or lower.

In a refrigeration cycle in which Refrigerant 1 according to the presentdisclosure is used, the evaporation pressure is preferably 0.02 MPa ormore, more preferably 0.03 MPa or more, even more preferably 0.04 MPa ormore, and particularly preferably 0.05 MPa or more, from the viewpointof improving the suction of the refrigerant into a compressor.

In a refrigeration cycle in which Refrigerant 1 according to the presentdisclosure is used, the compression ratio is preferably 2.5 or more,more preferably 3.0 or more, even more preferably 3.5 or more, andparticularly preferably 4.0 or more, from the viewpoint of improving theefficiency of the refrigeration cycle. In a refrigeration cycle in whichRefrigerant 1 according to the present disclosure is used, thecompression ratio is preferably 200 or less, more preferably 150 orless, even more preferably 100 or less, and particularly preferably 50or less, from the viewpoint of improving the efficiency of therefrigeration cycle.

Refrigerant 1 may comprise HFO-1132 (E) and HFO-1234yf in such amountsthat the sum of their concentrations is usually 99.5 mass % or more. Inthe present disclosure, the total amount of HFO-1132 (E) and HFO-1234yfis preferably 99.7 mass % or more, more preferably 99.8 mass % or more,and even more preferably 99.9 mass % or more, of entire Refrigerant 1.

Refrigerant 1 may further comprise an additional refrigerant in additionto HFO-1132 (E) and HFO-1234yf as long as the above characteristics arenot impaired. In this case, the content of the additional refrigerant ispreferably 0.5 mass % or less, more preferably 0.3 mass % or less, evenmore preferably 0.2 mass % or less, and particularly preferably 0.1 mass% or less, of entire Refrigerant 1. The additional refrigerant is notlimited and may be selected from a wide range of known refrigerantswidely used in the field. Refrigerant 1 may comprise one additionalrefrigerant or two or more additional refrigerants.

It is particularly preferred that Refrigerant 1 consist of HFO-1132 (E)and HFO-1234yf. In other words, the total concentration of HFO-1132 (E)and HFO-1234yf in Refrigerant 1 is particularly preferably 100 mass % ofentire Refrigerant 1.

When Refrigerant 1 consists of HFO-1132 (E) and HFO-1234yf, HFO-1132 (E)is usually present in an amount of 35.0 to 65.0 mass %, and HFO-1234yfis usually present in an amount of 65.0 to 35.0 mass %, based on thetotal mass of HFO-1132 (E) and HFO-1234yf. Refrigerant 1 has the abovefeature and thus has the following characteristics: (1) the GWP issufficiently low (100 or less); (2) it has a COP equivalent to or higherthan that of R404A; and (3) it has a refrigerating capacity equivalentto or higher than that of R404A.

When Refrigerant 1 consists of HFO-1132 (E) and HFO-1234yf, it ispreferred that HFO-1132 (E) be present in an amount of 40.5 to 59.0 mass%, and HFO-1234yf be present in an amount of 59.5 to 41.0 mass %, basedon the total mass of HFO-1132 (E) and HFO-1234yf. In this case,Refrigerant 1 has a GWP of 100 or less, a COP of 101% or more relativeto that of R404A, and a refrigerating capacity of 99% or more relativeto that of R404A. Further, in this case, Refrigerant 1 has a saturationpressure of 1.75 MPa or more and 2.00 MPa or less at a saturationtemperature of 40° C., and is thus applicable to commercially availablerefrigeration apparatuses for R404A without significant design change.

When Refrigerant 1 consists of HFO-1132 (E) and HFO-1234yf, it ispreferred that HFO-1132 (E) be present in an amount of 41.3 to 59.0 mass%, and HFO-1234yf be present in an amount of 58.7 to 41.0 mass %, basedon the total mass of HFO-1132 (E) and HFO-1234yf. In this case,Refrigerant 1 has a GWP of 100 or less, a COP of 101% or more relativeto that of R404A, and a refrigerating capacity of 99.5% or more relativeto that of R404A. Further, in this case, Refrigerant 1 has a saturationpressure of 1.76 MPa or more and 2.00 MPa or less at a saturationtemperature of 40° C., and is thus applicable to commercially availablerefrigeration apparatuses for R404A without significant design change.

When Refrigerant 1 consists of HFO-1132 (E) and HFO-1234yf, it isfurther preferred that HFO-1132 (E) be present in an amount of 41.3 to55.0 mass %, and HFO-1234yf be present in an amount of 58.7 to 45.0 mass%, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case,Refrigerant 1 has a GWP of 100 or less, a COP of 101% or more relativeto that of R404A, and a refrigerating capacity of 99.5% or more relativeto that of R404A. Further, in this case, Refrigerant 1 has a saturationpressure of 1.76 MPa or more and 1.95 MPa or less at a saturationtemperature of 40° C., and is thus applicable to commercially availablerefrigeration apparatuses for R404A without significant design change.

When Refrigerant 1 consists of HFO-1132 (E) and HFO-1234yf, it isparticularly preferred that HFO-1132 (E) be present in an amount of 41.3to 53.5 mass %, and HFO-1234yf be present in an amount of 58.7 to 46.5mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In thiscase, Refrigerant 1 has characteristics of having a GWP of 100 or less,a COP of 102% or more relative to that of R404A, and a refrigeratingcapacity of 99.5% or more relative to that of R404A, as well as beingslightly flammable according to ASHRAE Standards (Class 2L). Further, inthis case, Refrigerant 1 has a saturation pressure of 1.76 MPa or moreand 1.94 MPa or less at a saturation temperature of 40° C., and is thusapplicable to commercially available refrigeration apparatuses for R404Awithout significant design change.

When Refrigerant 1 consists of HFO-1132 (E) and HFO-1234yf, it isparticularly preferred that HFO-1132 (E) be present in an amount of 41.3to 51.0 mass %, and HFO-1234yf be present in an amount of 58.7 to 49.0mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In thiscase, Refrigerant 1 has characteristics of having a GWP of 100 or less,a COP of 102% or more relative to that of R404A, and a refrigeratingcapacity of 99% or more relative to that of R404A, as well as beingslightly flammable according to ASHRAE Standards (Class 2L). Further, inthis case, Refrigerant 1 has a saturation pressure of 1.76 MPa or moreand 1.90 MPa or less at a saturation temperature of 40° C., and is thusapplicable to commercially available refrigeration apparatuses for R404Awithout significant design change.

When Refrigerant 1 consists of HFO-1132 (E) and HFO-1234yf, it is mostpreferred that HFO-1132 (E) be present in an amount of 41.3 to 49.2 mass%, and HFO-1234yf be present in an amount of 58.7 to 50.8 mass %, basedon the total mass of HFO-1132 (E) and HFO-1234yf. In this case,Refrigerant 1 has characteristics of having a GWP of 100 or less, a COPof 102% or more relative to that of R404A, and a refrigerating capacityof 99.5% or more relative to that of R404A, as well as being slightlyflammable according to ASHRAE Standards (Class 2L). Further, in thiscase, Refrigerant 1 has a saturation pressure of 1.76 MPa or more and1.88 MPa or less at a saturation temperature of 40° C., and is thusapplicable to commercially available refrigeration apparatuses for R404Awithout significant design change.

1.2 Refrigerant 2

In an embodiment, the refrigerant contained in the composition accordingto the present disclosure comprises HFO-1132 (E) and HFO-1234yf, whereinHFO-1132 (E) is present in an amount of 40.5 to 49.2 mass %, andHFO-1234yf is present in an amount of 59.5 to 50.8 mass %, based on thetotal mass of HFO-1132 (E) and HFO-1234yf. This refrigerant may bereferred to as “Refrigerant 2.”

Refrigerant 2 has the above feature and thus has the followingcharacteristics: (1) the GWP is sufficiently low (100 or less); (2) ithas a COP equivalent to or higher than that of R404A; (3) it has arefrigerating capacity equivalent to or higher than that of R404A; and(4) it is slightly flammable according to ASHRAE Standards (Class 2L).Further, in this case, Refrigerant 2 has a saturation pressure of 1.75MPa or more and 1.88 MPa or less at a saturation temperature of 40° C.,and is thus applicable to commercially available refrigerationapparatuses for R404A without significant design change.

Since Refrigerant 2 comprises HFO-1132 (E) in an amount of 40.5 mass %or more based on the total mass of HFO-1132 (E) and HFO-1234yf,Refrigerant 2 has a refrigerating capacity equivalent to or higher thanthat of R404A. Moreover, since Refrigerant 2 comprises HFO-1132 (E) inan amount of 49.2 mass % or less based on the total mass of HFO-1132 (E)and HFO-1234yf, the saturation pressure of Refrigerant 2 at a saturationtemperature of 40° C. in the refrigeration cycle can be maintainedwithin a suitable range (in particular 2.10 Mpa or less).

Refrigerant 2 may have a refrigerating capacity of 99% or more,preferably 100% or more, more preferably 101% or more, even morepreferably 102% or more, and particularly preferably 103% or more,relative to that of R404A.

Since the GWP is 100 or less, Refrigerant 2 can notably reduce theburden on the environment from a global warming perspective, comparedwith other general-purpose refrigerants.

In Refrigerant 2, the ratio of refrigerating capacity to power consumedin a refrigeration cycle (coefficient of performance (COP)) relative tothat of R404A is preferably high, from the viewpoint of energyconsumption efficiency. Specifically, the COP relative to that of R404Ais preferably 98% or more, more preferably 100% or more, even morepreferably 101% or more, and particularly preferably 102% or more.

In Refrigerant 2, it is preferred that HFO-1132 (E) be present in anamount of 41.3 to 49.2 mass %, and HFO-1234yf be present in an amount of58.7 to 50.8 mass %, based on the total mass of HFO-1132 (E) andHFO-1234yf. In this case, Refrigerant 2 has characteristics of having aGWP of 100 or less, a COP of 102% or more relative to that of R404A, anda refrigerating capacity of 99.5% or more relative to that of R404A, aswell as being slightly flammable according to ASHRAE Standards (Class2L). Further, in this case, Refrigerant 2 has a saturation pressure of1.76 MPa or more and 1.88 MPa or less at a saturation temperature of 40°C., and is thus applicable to commercially available refrigerationapparatuses for R404A without significant design change.

In Refrigerant 2, it is preferred that HFO-1132 (E) be present in anamount of 43.0 to 49.2 mass %, and HFO-1234yf be present in an amount of57.0 to 50.8 mass %, based on the total mass of HFO-1132 (E) andHFO-1234yf. In this case, Refrigerant 2 has characteristics of having aGWP of 100 or less, a COP of 102% or more relative to that of R404A, anda refrigerating capacity of 101% or more relative to that of R404A, aswell as being slightly flammable according to ASHRAE Standards (Class2L). Further, in this case, Refrigerant 2 has a saturation pressure of1.78 MPa or more and 1.88 MPa or less at a saturation temperature of 40°C., and is thus applicable to commercially available refrigerationapparatuses for R404A without significant design change.

In Refrigerant 2, it is further preferred that HFO-1132 (E) be presentin an amount of 44.0 to 49.2 mass %, and HFO-1234yf be present in anamount of 56.0 to 50.8 mass %, based on the total mass of HFO-1132 (E)and HFO-1234yf. In this case, Refrigerant 2 has characteristics ofhaving a GWP of 100 or less, a COP of 102% or more relative to that ofR404A, and a refrigerating capacity of 101% or more relative to that ofR404A, as well as being slightly flammable according to ASHRAE Standards(Class 2L). Further, in this case, Refrigerant 2 has a saturationpressure of 1.80 MPa or more and 1.88 MPa or less at a saturationtemperature of 40° C., and is thus applicable to commercially availablerefrigeration apparatuses for R404A without significant design change.

In Refrigerant 2, it is particularly preferred that HFO-1132 (E) bepresent in an amount of 45.0 to 49.2 mass %, and HFO-1234yf be presentin an amount of 55.0 to 50.8 mass %, based on the total mass of HFO-1132(E) and HFO-1234yf. In this case, Refrigerant 2 has characteristics ofhaving a GWP of 100 or less, a COP of 102% or more relative to that ofR404A, and a refrigerating capacity of 102% or more relative to that ofR404A, as well as being slightly flammable according to ASHRAE Standards(Class 2L). Further, in this case, Refrigerant 2 has a saturationpressure of 1.81 MPa or more and 1.88 MPa or less at a saturationtemperature of 40° C., and is thus applicable to commercially availablerefrigeration apparatuses for R404A without significant design change.

In Refrigerant 2, it is particularly preferred that HFO-1132 (E) bepresent in an amount of 45.0 to 48.0 mass %, and HFO-1234yf be presentin an amount of 55.0 to 52.0 mass %, based on the total mass of HFO-1132(E) and HFO-1234yf. In this case, Refrigerant 2 has characteristics ofhaving a GWP of 100 or less, a COP of 102.5% or more relative to that ofR404A, and a refrigerating capacity of 102.5% or more relative to thatof R404A, as well as being slightly flammable according to ASHRAEStandards (Class 2L). Further, in this case, Refrigerant 2 has asaturation pressure of 1.81 MPa or more and 1.87 MPa or less at asaturation temperature of 40° C., and is thus applicable to commerciallyavailable refrigeration apparatuses for R404A without significant designchange.

In Refrigerant 2, it is most preferred that HFO-1132 (E) be present inan amount of 45.0 to 47.0 mass %, and HFO-1234yf be present in an amountof 55.0 to 53.0 mass %, based on the total mass of HFO-1132 (E) andHFO-1234yf. In this case, Refrigerant 2 has characteristics of having aGWP of 100 or less, a COP of 102.5% or more relative to that of R404A,and a refrigerating capacity of 102.5% or more relative to that ofR404A, as well as being slightly flammable according to ASHRAE Standards(Class 2L). Further, in this case, Refrigerant 2 has a saturationpressure of 1.81 MPa or more and 1.85 MPa or less at a saturationtemperature of 40° C., and is thus applicable to commercially availablerefrigeration apparatuses for R404A without significant design change.

In Refrigerant 2, the saturation pressure at a saturation temperature of40° C. is usually 2.10 MPa or less, preferably 2.00 MPa or less, morepreferably 1.95 MPa or less, even more preferably 1.90 MPa or less, andparticularly preferably 1.88 MPa or less. If the saturation pressure ata saturation temperature of 40° C. is within the above range,Refrigerant 2 is applicable to commercially available refrigerationapparatuses for R404A without significant design change.

In Refrigerant 2, the saturation pressure at a saturation temperature of40° C. is usually 1.70 MPa or more, preferably 1.73 MPa or more, morepreferably 1.74 MPa or more, even more preferably 1.75 MPa or more, andparticularly preferably 1.76 MPa or more. If the saturation pressure ata saturation temperature of 40° C. is within the above range,Refrigerant 2 is applicable to commercially available refrigerationapparatuses for R404A without significant design change.

In the present disclosure, when Refrigerant 2 is used for operating arefrigeration cycle, the discharge temperature is preferably 150° C. orlower, more preferably 140° C. or lower, even more preferably 130° C. orlower, and particularly preferably 120° C. or lower, from the viewpointof extending the life of the components of a commercially availablerefrigeration apparatus for R404A.

In the present disclosure, Refrigerant 2 is preferably used foroperating a refrigeration cycle in which the evaporation temperature is−75 to 15° C. from the viewpoint of obtaining a refrigerating capacityequivalent to or higher than that of R404A.

In a refrigeration cycle in which Refrigerant 2 according to the presentdisclosure is used, the evaporation temperature is preferably 15° C. orlower, more preferably 5° C. or lower, even more preferably 0° C. orlower, and particularly preferably −5° C. or lower.

In a refrigeration cycle in which Refrigerant 2 according to the presentdisclosure is used, the evaporation temperature is preferably −65° C. ormore, more preferably −60° C. or more, even more preferably −55° C. ormore, and particularly preferably −50° C. or more.

In a refrigeration cycle in which Refrigerant 2 according to the presentdisclosure is used, the evaporation temperature is preferably −65° C. ormore and 10° C. or lower, more preferably −60° C. or more and 5° C. orlower, even more preferably −55° C. or more and 0° C. or lower, andparticularly preferably −50° C. or more and −5° C. or lower.

In a refrigeration cycle in which Refrigerant 2 according to the presentdisclosure is used, the evaporation pressure is preferably 0.02 MPa ormore, more preferably 0.03 MPa or more, even more preferably 0.04 MPa ormore, and particularly preferably 0.05 MPa or more, from the viewpointof improving the suction of the refrigerant into a compressor.

In a refrigeration cycle in which Refrigerant 2 according to the presentdisclosure is used, the compression ratio is preferably 2.5 or more,more preferably 3.0 or more, even more preferably 3.5 or more, andparticularly preferably 4.0 or more, from the viewpoint of improving theefficiency of the refrigeration cycle.

Refrigerant 2 may comprise HFO-1132 (E) and HFO-1234yf in such amountsthat the sum of their concentrations is usually 99.5 mass % or more. Inthe present disclosure, the total amount of HFO-1132 (E) and HFO-1234yfis preferably 99.7 mass % or more, more preferably 99.8 mass % or more,and even more preferably 99.9 mass % or more, of entire Refrigerant 2.

Refrigerant 2 may further comprise an additional refrigerant in additionto HFO-1132 (E) and HFO-1234yf as long as the above characteristics arenot impaired. In this case, the content of the additional refrigerant ispreferably 0.5 mass % or less, more preferably 0.3 mass % or less, evenmore preferably 0.2 mass % or less, and particularly preferably 0.1 mass% or less, of entire Refrigerant 2. The additional refrigerant is notlimited and may be selected from a wide range of known refrigerantswidely used in the field. Refrigerant 2 may comprise one additionalrefrigerant or two or more additional refrigerants.

It is particularly preferred that Refrigerant 2 consist of HFO-1132 (E)and HFO-1234yf. In other words, the total concentration of HFO-1132 (E)and HFO-1234yf in Refrigerant 2 is particularly preferably 100 mass % ofentire Refrigerant 2.

When Refrigerant 2 consists of HFO-1132 (E) and HFO-1234yf, HFO-1132 (E)is usually present in an amount of 40.5 to 49.2 mass %, and HFO-1234yfis usually present in an amount of 59.5 to 50.8 mass %, based on thetotal mass of HFO-1132 (E) and HFO-1234yf. Refrigerant 2 has the abovefeature and thus has the following characteristics: (1) the GWP issufficiently low (100 or less); (2) it has a COP equivalent to or higherthan that of R404A; (3) it has a refrigerating capacity equivalent to orhigher than that of R404A; and (4) it is slightly flammable according toASHRAE Standards (Class 2L). Further, in this case, Refrigerant 2 has asaturation pressure of 1.75 MPa or more and 1.88 MPa or less at asaturation temperature of 40° C., and is thus applicable to commerciallyavailable refrigeration apparatuses for R404A without significant designchange.

When Refrigerant 2 consists of HFO-1132 (E) and HFO-1234yf, it ispreferred that HFO-1132 (E) be present in an amount of 41.3 to 49.2 mass%, and HFO-1234yf be present in an amount of 58.7 to 50.8 mass %, basedon the total mass of HFO-1132 (E) and HFO-1234yf. In this case,Refrigerant 2 has characteristics of having a GWP of 100 or less, a COPof 102% or more relative to that of R404A, and a refrigerating capacityof 99.5% or more relative to that of R404A, as well as being slightlyflammable according to ASHRAE Standards (Class 2L). Further, in thiscase, Refrigerant 2 has a saturation pressure of 1.76 MPa or more and1.88 MPa or less at a saturation temperature of 40° C., and is thusapplicable to commercially available refrigeration apparatuses for R404Awithout significant design change.

When Refrigerant 2 consists of HFO-1132 (E) and HFO-1234yf, it ispreferred that HFO-1132 (E) be present in an amount of 43.0 to 49.2 mass%, and HFO-1234yf be present in an amount of 57.0 to 50.8 mass %, basedon the total mass of HFO-1132 (E) and HFO-1234yf. In this case,Refrigerant 2 has characteristics of having a GWP of 100 or less, a COPof 102% or more relative to that of R404A, and a refrigerating capacityof 101% or more relative to that of R404A, as well as being slightlyflammable according to ASHRAE Standards (Class 2L). Further, in thiscase, Refrigerant 2 has a saturation pressure of 1.78 MPa or more and1.88 MPa or less at a saturation temperature of 40° C., and is thusapplicable to commercially available refrigeration apparatuses for R404Awithout significant design change.

When Refrigerant 2 consists of HFO-1132 (E) and HFO-1234yf, it isfurther preferred that HFO-1132 (E) be present in an amount of 44.0 to49.2 mass %, and HFO-1234yf be present in an amount of 56.0 to 50.8 mass%, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case,Refrigerant 2 has characteristics of having a GWP of 100 or less, a COPof 102% or more relative to that of R404A, and a refrigerating capacityof 101% or more relative to that of R404A, as well as being slightlyflammable according to ASHRAE Standards (Class 2L). Further, in thiscase, Refrigerant 2 has a saturation pressure of 1.80 MPa or more and1.88 MPa or less at a saturation temperature of 40° C., and is thusapplicable to commercially available refrigeration apparatuses for R404Awithout significant design change.

When Refrigerant 2 consists of HFO-1132 (E) and HFO-1234yf, it isparticularly preferred that HFO-1132 (E) be present in an amount of 45.0to 49.2 mass %, and HFO-1234yf be present in an amount of 55.0 to 50.8mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In thiscase, Refrigerant 2 has characteristics of having a GWP of 100 or less,a COP of 102% or more relative to that of R404A, and a refrigeratingcapacity of 102% or more relative to that of R404A, as well as beingslightly flammable according to ASHRAE Standards (Class 2L). Further, inthis case, Refrigerant 2 has a saturation pressure of 1.81 MPa or moreand 1.88 MPa or less at a saturation temperature of 40° C., and is thusapplicable to commercially available refrigeration apparatuses for R404Awithout significant design change.

When Refrigerant 2 consists of HFO-1132 (E) and HFO-1234yf, it isparticularly preferred that HFO-1132 (E) be present in an amount of 45.0to 48.0 mass %, and HFO-1234yf be present in an amount of 55.0 to 52.0mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In thiscase, Refrigerant 2 has characteristics of having a GWP of 100 or less,a COP of 102.5% or more relative to that of R404A, and a refrigeratingcapacity of 102.5% or more relative to that of R404A, as well as beingslightly flammable according to ASHRAE Standards (Class 2L). Further, inthis case, Refrigerant 2 has a saturation pressure of 1.81 MPa or moreand 1.87 MPa or less at a saturation temperature of 40° C., and is thusapplicable to commercially available refrigeration apparatuses for R404Awithout significant design change.

1.3 Refrigerant 3

In an embodiment, the refrigerant contained in the composition accordingto the present disclosure comprises HFO-1132 (E) and HFO-1234yf, whereinHFO-1132 (E) is present in an amount of 31.1 to 39.8 mass %, andHFO-1234yf is present in an amount of 68.9 to 60.2 mass %, based on thetotal mass of HFO-1132 (E) and HFO-1234yf. This refrigerant may bereferred to as “Refrigerant 3.”

Refrigerant 3 has the above feature and thus has the followingcharacteristics: (1) the GWP is sufficiently low (100 or less); (2) ithas a COP almost equivalent to that of R134a; (3) it has a refrigeratingcapacity of 150% or more relative to that of R134a; and (4) thedischarge temperature is 90° C. or less.

Since Refrigerant 3 comprises HFO-1132 (E) in an amount of 31.1 mass %or more based on the total mass of HFO-1132 (E) and HFO-1234yf,Refrigerant 3 has a refrigerating capacity of 150% or more relative tothat of R134a. Moreover, since Refrigerant 3 comprises HFO-1132 (E) inan amount of 39.8 mass % or less based on the total mass of HFO-1132 (E)and HFO-1234yf, the discharge temperature of Refrigerant 3 in arefrigeration cycle can be maintained at 90° C. or less, and long lifeof the components of a refrigeration apparatus for R134a can be ensured.

Refrigerant 3 may have a refrigerating capacity of 150% or more,preferably 151% or more, more preferably 152% or more, even morepreferably 153% or more, and particularly preferably 154% or more,relative to that of R134a.

Refrigerant 3 has a discharge temperature of preferably 90.0° C. orless, more preferably 89.7° C. or less, even more preferably 89.4° C. orless, and particularly preferably 89.0° C. or less, in a refrigerationcycle.

Since the GWP is 100 or less, Refrigerant 3 can notably reduce theburden on the environment from a global warming perspective, comparedwith other general-purpose refrigerants.

In Refrigerant 3, the ratio of refrigerating capacity to power consumedin a refrigeration cycle (coefficient of performance (COP)) relative tothat of R134a is preferably high, from the viewpoint of energyconsumption efficiency. Specifically, the COP relative to that of R134ais preferably 90% or more, more preferably 91% or more, even morepreferably 91.5% or more, and particularly preferably 92% or more.

In Refrigerant 3, HFO-1132 (E) is usually present in an amount of 31.1to 39.8 mass %, and HFO-1234yf is usually present in an amount of 68.9to 60.2 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf.Refrigerant 3 has the above feature and thus has the followingcharacteristics: (1) the GWP is sufficiently low (100 or less); (2) ithas a COP almost equivalent to that of R134a; (3) it has a refrigeratingcapacity of 150% or more relative to that of R134a; and (4) thedischarge temperature is 90.0° C. or less.

In Refrigerant 3, it is preferred that HFO-1132 (E) be present in anamount of 31.1 to 37.9 mass %, and HFO-1234yf be present in an amount of68.9 to 62.1 mass %, based on the total mass of HFO-1132 (E) andHFO-1234yf. In this case, Refrigerant 3 has the above feature and thushas the following characteristics: (1) the GWP is sufficiently low (100or less); (2) it has an COP of 92% or more relative to that of R134a;(3) it has a refrigerating capacity of 150% or more relative to that ofR134a; (4) the discharge temperature is 90.0° C. or less; and (5) thecritical temperature is 81° C. or more.

In Refrigerant 3, it is more preferred that HFO-1132 (E) be present inan amount of 32.0 to 37.9 mass %, and HFO-1234yf be present in an amountof 68.0 to 62.1 mass %, based on the total mass of HFO-1132 (E) andHFO-1234yf. In this case, Refrigerant 3 has the above feature and thushas the following characteristics: (1) the GWP is sufficiently low (100or less); (2) it has a COP of 92% or more relative to that of R134a; (3)it has a refrigerating capacity of 151% or more relative to that ofR134a; (4) the discharge temperature is 90.0° C. or less, and (5) thecritical temperature is 81° C. or more.

In Refrigerant 3, it is further preferred that HFO-1132 (E) be presentin an amount of 33.0 to 37.9 mass %, and HFO-1234yf be present in anamount of 67.0 to 62.1 mass %, based on the total mass of HFO-1132 (E)and HFO-1234yf. In this case, Refrigerant 3 has the above feature andthus has the following characteristics: (1) the GWP is sufficiently low(100 or less); (2) it has a COP of 92% or more relative to that ofR134a; (3) it has a refrigerating capacity of 152% or more relative tothat of R134a; (4) the discharge temperature is 90.0° C. or less; and(5) the critical temperature is 81° C. or more.

In Refrigerant 3, it is even more preferred that HFO-1132 (E) be presentin an amount of 34.0 to 37.9 mass %, and HFO-1234yf be present in anamount of 66.0 to 62.1 mass %, based on the total mass of HFO-1132 (E)and HFO-1234yf. In this case, Refrigerant 3 has the above feature andthus has the following characteristics: (1) the GWP is sufficiently low(100 or less); (2) it has a COP of 92% or more relative to that ofR134a; (3) it has a refrigerating capacity of 153% or more relative tothat of R134a; (4) the discharge temperature is 90.0° C. or less; and(5) the critical temperature is 81° C. or more.

In Refrigerant 3, it is particularly preferred that HFO-1132 (E) bepresent in an amount of 35.0 to 37.9 mass %, and HFO-1234yf be presentin an amount of 65.0 to 62.1 mass %, based on the total mass of HFO-1132(E) and HFO-1234yf. In this case, Refrigerant 3 has the above featureand thus has the following characteristics: (1) the GWP is sufficientlylow (100 or less); (2) it has a COP of 92% or more relative to that ofR134a; (3) it has a refrigerating capacity of 155% or more relative tothat of R134a; (4) the discharge temperature is 90.0° C. or less; and(5) the critical temperature is 81° C. or more.

In the present disclosure, when Refrigerant 3 is used for operating arefrigeration cycle, the discharge temperature is preferably 90.0° C. orless, more preferably 89.7° C. or less, even more preferably 89.4° C. orless, and particularly preferably 89.0° C. or less, from the viewpointof extending the life of the components of a commercially availablerefrigeration apparatus for R134a.

In the present disclosure, when Refrigerant 3 is used for operating arefrigeration cycle, the refrigeration cycle requires the process ofliquefying (condensing) the refrigerant; thus, the critical temperatureneeds to be notably higher than the temperature of cooling water orcooling air for liquefying the refrigerant. From this viewpoint, in arefrigeration cycle in which Refrigerant 3 according to the presentdisclosure is used, the critical temperature is preferably 80° C. ormore, more preferably 81° C. or more, even more preferably 81.5° C. ormore, and particularly preferably 82° C. or more.

In the present disclosure, Refrigerant 3 is usually used for operating arefrigeration cycle in which the evaporation temperature is −75 to 15°C., from the viewpoint of obtaining a refrigerating capacity of 150% ormore relative to that of R134a.

In a refrigeration cycle in which Refrigerant 3 according to the presentdisclosure is used, the evaporation temperature is preferably 15° C. orless, more preferably 5° C. or less, even more preferably 0° C. or less,and particularly preferably −5° C. or less.

In a refrigeration cycle in which Refrigerant 3 according to the presentdisclosure is used, the evaporation temperature is preferably −65° C. ormore, more preferably −60° C. or more, even more preferably −55° C. ormore, and particularly preferably −50° C. or more.

In a refrigeration cycle in which Refrigerant 3 according to the presentdisclosure is used, the evaporation temperature is preferably −65° C. ormore and 15° C. or less, more preferably −60° C. or more and 5° C. orless, even more preferably-55° C. or more and 0° C. or less, andparticularly preferably −50° C. or more and −5° C. or less.

In a refrigeration cycle in which Refrigerant 3 according to the presentdisclosure is used, the critical temperature of the refrigerant ispreferably 80° C. or more, more preferably 81° C. or more, even morepreferably 81.5° C. or more, and particularly preferably 82° C. or more,from the viewpoint of improving the performance.

Refrigerant 3 may comprise HFO-1132 (E) and HFO-1234yf in such amountsthat the sum of their concentrations is usually 99.5 mass % or more. Inthe present disclosure, the total amount of HFO-1132 (E) and HFO-1234yfis preferably 99.7 mass % or more, more preferably 99.8 mass % or more,and even more preferably 99.9 mass % or more, of entire Refrigerant 3.

Refrigerant 3 may further comprise an additional refrigerant in additionto HFO-1132 (E) and HFO-1234yf as long as the above characteristics arenot impaired. In this case, the content of the additional refrigerant ispreferably 0.5 mass % or less, more preferably 0.3 mass % or less, evenmore preferably 0.2 mass % or less, and particularly preferably 0.1 mass% or less, of entire Refrigerant 3. The additional refrigerant is notlimited and may be selected from a wide range of known refrigerantswidely used in the field. Refrigerant 3 may comprise one additionalrefrigerant or two or more additional refrigerants.

It is particularly preferred that Refrigerant 3 consist of HFO-1132 (E)and HFO-1234yf. In other words, the total concentration of HFO-1132 (E)and HFO-1234yf in Refrigerant 3 is particularly preferably 100 mass % ofentire Refrigerant 3.

When Refrigerant 3 consists of HFO-1132 (E) and HFO-1234yf, HFO-1132 (E)is usually present in an amount of 31.1 to 39.8 mass %, and HFO-1234yfis usually present in an amount of 68.9 to 60.2 mass %, based on thetotal mass of HFO-1132 (E) and HFO-1234yf. Refrigerant 3 has the abovefeature and thus has the following characteristics: (1) the GWP issufficiently low (100 or less); (2) it has a COP almost equivalent tothat of R134a; (3) it has a refrigerating capacity of 150% or morerelative to that of R134a; and (4) the discharge temperature is 90° C.or less.

When Refrigerant 3 consists of HFO-1132 (E) and HFO-1234yf, it ispreferred that HFO-1132 (E) be present in an amount of 31.1 to 37.9 mass%, and HFO-1234yf be present in an amount of 68.9 to 62.1 mass %, basedon the total mass of HFO-1132 (E) and HFO-1234yf. In this case,Refrigerant 3 has the above feature and thus has the followingcharacteristics: (1) the GWP is sufficiently low (100 or less); (2) ithas a COP of 92% or more relative to that of R134a; (3) it has arefrigerating capacity of 150% or more relative to that of R134a; (4)the discharge temperature is 90.0° C. or less; and (5) the criticaltemperature is 81° C. or more.

When Refrigerant 3 consists of HFO-1132 (E) and HFO-1234yf, it is morepreferred that HFO-1132 (E) be present in an amount of 32.0 to 37.9 mass%, and HFO-1234yf be present in an amount of 68.0 to 62.1 mass %, basedon the total mass of HFO-1132 (E) and HFO-1234yf. In this case,Refrigerant 3 has the above feature and thus has the followingcharacteristics: (1) the GWP is sufficiently low (100 or less); (2) ithas a COP of 92% or more relative to that of R134a; (3) it has arefrigerating capacity of 151% or more relative to that of R134a; (4)the discharge temperature is 90.0° C. or less; and (5) the criticaltemperature is 81° C. or more.

When Refrigerant 3 consists of HFO-1132 (E) and HFO-1234yf, it is evenmore preferred that HFO-1132 (E) be present in an amount of 33.0 to 37.9mass %, and HFO-1234yf be present in an amount of 67.0 to 62.1 mass %,based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case,Refrigerant 3 has the above feature and thus has the followingcharacteristics: (1) the GWP is sufficiently low (100 or less); (2) ithas a COP of 92% or more relative to that of R134a; (3) it has arefrigerating capacity of 152% or more relative to that of R134a; (4)the discharge temperature is 90.0° C. or less; and (5) the criticaltemperature is 81° C. or more.

When Refrigerant 3 consists of HFO-1132 (E) and HFO-1234yf, it isfurther preferred that HFO-1132 (E) be present in an amount of 34.0 to37.9 mass %, and HFO-1234yf be present in an amount of 66.0 to 62.1 mass%, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case,Refrigerant 3 has the above feature and thus has the followingcharacteristics: (1) the GWP is sufficiently low (100 or less); (2) ithas a COP of 92% or more relative to that of R134a; (3) it has arefrigerating capacity of 153% or more relative to that of R134a; (4)the discharge temperature is 90.0° C. or less; and (5) the criticaltemperature is 81° C. or more.

When Refrigerant 3 consists of HFO-1132 (E) and HFO-1234yf, it isparticularly preferred that HFO-1132(E) be present in an amount of 35.0to 37.9 mass %, and HFO-1234yf be present in an amount of 65.0 to 62.1mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In thiscase, Refrigerant 3 has the above feature and thus has the followingcharacteristics: (1) the GWP is sufficiently low (100 or less); (2) ithas a COP of 92% or more relative to that of R134a; (3) it has arefrigerating capacity of 155% or more relative to that of R134a; (4)the discharge temperature is 90.0° C. or less; and (5) the criticaltemperature is 81° C. or more.

1.4 Refrigerant 4

In an embodiment, the refrigerant contained in the composition accordingto the present disclosure comprises HFO-1132 (E) and HFO-1234yf, whereinHFO-1132 (E) is present in an amount of 21.0 to 28.4 mass %, andHFO-1234yf is present in an amount of 79.0 to 71.6 mass %, based on thetotal mass of HFO-1132 (E) and HFO-1234yf. This refrigerant may bereferred to as “Refrigerant 4.”

Refrigerant 4 has the above feature and thus has the followingcharacteristics: (1) the GWP is sufficiently low (100 or less); (2) ithas a COP almost equivalent to that of R1234yf; (3) it has arefrigerating capacity of 140% or more relative to that of R1234yf; and(4) it is slightly flammable according to ASHRAE standards (Class 2L).Further, in this case, Refrigerant 4 has a saturation pressure of 0.380MPa or more and 0.420 MPa or less at a saturation temperature of −10°C., and is thus applicable to commercially available refrigerationapparatuses for R1234yf without significant design change.

Since Refrigerant 4 comprises HFO-1132 (E) in an amount of 21.0 mass %or more based on the total mass of HFO-1132 (E) and HFO-1234yf,Refrigerant 4 has a refrigerating capacity of 140% or more relative tothat of R1234yf. Moreover, Refrigerant 4 comprises HFO-1132 (E) in anamount of 28.4 mass % or less based on the total mass of HFO-1132 (E)and HFO-1234yf. This makes it easy to ensure a critical temperature of83.5° C. or more.

Refrigerant 4 may have a refrigerating capacity of 140% or more,preferably 142% or more, more preferably 143% or more, even morepreferably 145% or more, and particularly preferably 146% or more,relative to that of R1234yf.

Since the GWP is 100 or less, Refrigerant 4 can notably reduce theburden on the environment from a global warming perspective, comparedwith other general-purpose refrigerants.

In Refrigerant 4, the ratio of refrigerating capacity to power consumedin a refrigeration cycle (coefficient of performance (COP)) relative tothat of R1234yf is preferably high from the viewpoint of energyconsumption efficiency. Specifically, the COP relative to that ofR1234yf is preferably 95% or more, more preferably 96% or more, evenmore preferably 97% or more, and particularly preferably 98% or more.

In Refrigerant 4, it is preferred that HFO-1132 (E) be present in anamount of 21.5 to 28.0 mass %, and HFO-1234yf be present in an amount of78.5 to 72.0 mass %, based on the total mass of HFO-1132 (E) andHFO-1234yf. In this case, Refrigerant 4 has the followingcharacteristics: the GWP is 100 or less; it has a COP of 98% or morerelative to that of R1234yf; it has a refrigerating capacity of 140% ormore relative to that of R1234yf; it is slightly flammable according toASHRAE standards (Class 2L); the discharge temperature is 65.0° C. orless; and the critical temperature is 83.5° C. or more. Further, in thiscase, Refrigerant 4 has a saturation pressure of 0.383 MPa or more and0.418 MPa or less at a saturation temperature of −10° C., and is thusapplicable to commercially available refrigeration apparatuses forR1234yf without significant design change.

In Refrigerant 4, it is more preferred that HFO-1132 (E) be present inan amount of 22.0 to 27.7 mass %, and HFO-1234yf be present in an amountof 78.0 to 72.3 mass %, based on the total mass of HFO-1132 (E) andHFO-1234yf. In this case, Refrigerant 4 has the followingcharacteristics: the GWP is 100 or less; it has a COP of 98% or morerelative to that of R1234yf; it has a refrigerating capacity of 140% ormore relative to that of R1234yf; it is slightly flammable according toASHRAE standards (Class 2L); the discharge temperature is 65.0° C. orless; and the critical temperature is 83.5° C. or more. Further, in thiscase, Refrigerant 4 has a saturation pressure of 0.385 MPa or more and0.417 MPa or less at a saturation temperature of −10° C., and is thusapplicable to commercially available refrigeration apparatuses forR1234yf without significant design change.

In Refrigerant 4, it is even more preferred that HFO-1132 (E) be presentin an amount of 22.5 to 27.5 mass %, and HFO-1234yf be present in anamount of 77.5 to 72.5 mass %, based on the total mass of HFO-1132 (E)and HFO-1234yf. In this case, Refrigerant 4 has the followingcharacteristics: the GWP is 100 or less; it has a COP of 98% or morerelative to that of R1234yf; it has a refrigerating capacity of 140% ormore relative to that of R1234yf; it is slightly flammable according toASHRAE standards (Class 2L); the discharge temperature is 64.8° C. orless; and the critical temperature is 83.8° C. or more. Further, in thiscase, Refrigerant 4 has a saturation pressure of 0.388 MPa or more and0.414 MPa or less at a saturation temperature of −10° C., and is thusapplicable to commercially available refrigeration apparatuses forR1234yf without significant design change.

In Refrigerant 4, it is particularly preferred that HFO-1132 (E) bepresent in an amount of 23.0 to 27.2 mass %, and HFO-1234yf be presentin an amount of 77.0 to 72.8 mass %, based on the total mass of HFO-1132(E) and HFO-1234yf. In this case, Refrigerant 4 has the followingcharacteristics: the GWP is 100 or less; it has a COP of 98% or morerelative to that of R1234yf; it has a refrigerating capacity of 141% ormore relative to that of R1234yf; it is slightly flammable according toASHRAE standards (Class 2L); the discharge temperature is 64.8° C. orless; and the critical temperature is 83.8° C. or more. Further, in thiscase, Refrigerant 4 has a saturation pressure of 0.390 MPa or more and0.414 MPa or less at a saturation temperature of −10° C., and is thusapplicable to commercially available refrigeration apparatuses forR1234yf without significant design change.

In Refrigerant 4, it is further particularly preferred that HFO-1132 (E)be present in an amount of 23.5 to 27.0 mass %, and HFO-1234yf bepresent in an amount of 76.5 to 73.0 mass %, based on the total mass ofHFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 4 has thefollowing characteristics: the GWP is 100 or less; it has a COP of 98%or more relative to that of R1234yf; it has a refrigerating capacity of142% or more relative to that of R1234yf; it is slightly flammableaccording to ASHRAE standards (Class 2L); the discharge temperature is64.8° C. or less; and the critical temperature is 83.8° C. or more.Further, in this case, Refrigerant 4 has a saturation pressure of 0.390MPa or more and 0.414 MPa or less at a saturation temperature of −10°C., and is thus applicable to commercially available refrigerationapparatuses for R1234yf without significant design change.

In Refrigerant 4, it is most preferred that HFO-1132 (E) be present inan amount of 24.0 to 26.7 mass %, and HFO-1234yf be present in an amountof 76.0 to 73.3 mass %, based on the total mass of HFO-1132 (E) andHFO-1234yf. In this case, Refrigerant 4 has the followingcharacteristics: the GWP is 100 or less; it has a COP of 98% or morerelative to that of R1234yf; it has a refrigerating capacity of 144% ormore relative to that of R1234yf; it is slightly flammable according toASHRAE standards (Class 2L); the discharge temperature is 64.6° C. orless; and the critical temperature is 84.0° C. or more. Further, in thiscase, Refrigerant 4 has a saturation pressure of 0.396 MPa or more and0.411 MPa or less at a saturation temperature of −10° C., and is thusapplicable to commercially available refrigeration apparatuses forR1234yf without significant design change.

In Refrigerant 4, the saturation pressure at a saturation temperature of−10° C. is usually 0.420 MPa or less, preferably 0.418 MPa or less, morepreferably 0.417 MPa or less, even more preferably 0.415 MPa or less,and particularly preferably 0.413 MPa or less. When the saturationpressure is within this range, Refrigerant 4 is applicable tocommercially available refrigeration apparatuses for R1234yf withoutsignificant design change.

In Refrigerant 4, the saturation pressure at a saturation temperature of−10° C. is usually 0.380 MPa or more, preferably 0.385 MPa or more, morepreferably 0.390 MPa or more, even more preferably 0.400 MPa or more,and particularly preferably 0.410 MPa or more. In these cases,Refrigerant 4 is applicable to commercially available refrigerationapparatuses for R1234yf without significant design change.

In the present disclosure, when Refrigerant 4 is used for operating arefrigeration cycle, the discharge temperature is preferably 65° C. orless, more preferably 64.8° C. or less, even more preferably 64.7° C. orless, and particularly preferably 64.5° C. or less, from the viewpointof extending the life of the components of a commercially availablerefrigeration apparatus for R1234yf.

In the present disclosure, Refrigerant 4 is preferably used foroperating a refrigeration cycle in which the evaporation temperature is−75 to 20° C., from the viewpoint of obtaining a refrigerating capacityof 140% or more relative to that of R1234yf.

In a refrigeration cycle in which Refrigerant 4 according to the presentdisclosure is used, the evaporation temperature is preferably 20° C. orless, more preferably 15° C. or less, even more preferably 10° C. orless, and particularly preferably 5° C. or less, from the viewpoint ofobtaining a refrigerating capacity of 140% or more relative to that ofR1234yf.

In a refrigeration cycle in which Refrigerant 4 according to the presentdisclosure is used, the evaporation temperature is preferably −75° C. to20° C., more preferably −65° C. to 15° C., even more preferably −60° C.to 10° C., further preferably-55° C. to 7.5° C., and particularlypreferably −50° C. to 5° C., from the viewpoint of obtaining arefrigerating capacity of 140% or more relative to that of R1234yf.

In a refrigeration cycle in which Refrigerant 4 according to the presentdisclosure is used, the evaporation temperature is preferably −75° C. ormore and 20° C. or less, more preferably −65° C. or more and 10° C. orless, further preferably-60° C. or more and 5° C. or less, even morepreferably −55° C. or more and 0° C. or less, and particularlypreferably −50° C. or more and −5° C. or less, from the viewpoint ofobtaining a refrigerating capacity of 140% or more relative to that ofR1234yf.

In a refrigeration cycle in which Refrigerant 4 according to the presentdisclosure is used, the discharge temperature is preferably 65.0° C. orless, more preferably 64.9° C. or less, even more preferably 64.8° C. orless, and particularly preferably 64.7° C. or less, from the viewpointof extending the life of the components of a commercially availablerefrigeration apparatus for R1234yf.

In the present disclosure, when Refrigerant 4 is used for operating arefrigeration cycle, the refrigeration cycle requires the process ofliquefying (condensing) the refrigerant; thus, the critical temperatureneeds to be notably higher than the temperature of cooling water orcooling air for liquefying the refrigerant. From this viewpoint, in arefrigeration cycle in which Refrigerant 4 according to the presentdisclosure is used, the critical temperature is preferably 83.5° C. ormore, more preferably 83.8° C. or more, even more preferably 84.0° C. ormore, and particularly preferably 84.5° C. or more.

Refrigerant 4 may further comprise an additional refrigerant in additionto HFO-1132 (E) and HFO-1234yf as long as the above characteristics arenot impaired. In this case, the content of the additional refrigerant ispreferably 0.5 mass % or less, more preferably 0.3 mass % or less, evenmore preferably 0.2 mass % or less, and particularly preferably 0.1 mass% or less, of entire Refrigerant 4. The additional refrigerant is notlimited and may be selected from a wide range of known refrigerantswidely used in the field. Refrigerant 4 may comprise one additionalrefrigerant or two or more additional refrigerants.

It is particularly preferred that Refrigerant 4 consist of HFO-1132 (E)and HFO-1234yf. In other words, the total concentration of HFO-1132 (E)and HFO-1234yf in Refrigerant 4 is particularly preferably 100 mass % ofentire Refrigerant 4.

When Refrigerant 4 consists of HFO-1132 (E) and HFO-1234yf, HFO-1132 (E)is usually present in an amount of 21.0 to 28.4 mass %, and HFO-1234yfis usually present in an amount of 79.0 to 71.6 mass %, based on thetotal mass of HFO-1132 (E) and HFO-1234yf. Refrigerant 4 has the abovefeature and thus has the following characteristics: (1) the GWP issufficiently low (100 or less); (2) it has a COP almost equivalent tothat of R1234yf; (3) it has a refrigerating capacity of 140% or morerelative to that of R1234yf; and (4) it is slightly flammable accordingto ASHRAE standards (Class 2L). Further, in this case, Refrigerant 4 hasa saturation pressure of 0.380 MPa or more and 0.420 MPa or less at asaturation temperature of −10° C. and is thus applicable to commerciallyavailable refrigeration apparatuses for R1234yf without significantdesign change.

When Refrigerant 4 consists of HFO-1132 (E) and HFO-1234yf, it ispreferred that HFO-1132 (E) be present in an amount of 21.5 to 28.0 mass%, and HFO-1234yf be present in an amount of 78.5 to 72.0 mass %, basedon the total mass of HFO-1132 (E) and HFO-1234yf. In this case,Refrigerant 4 has the following characteristics: the GWP is 100 or less;it has a COP of 98% or more relative to that of R1234yf; it has arefrigerating capacity of 140% or more relative to that of R1234yf; itis slightly flammable according to ASHRAE standards (Class 2L); thedischarge temperature is 65.0° C. or less; and the critical temperatureis 83.5° C. or more. Further, in this case, Refrigerant 4 has asaturation pressure of 0.383 MPa or more and 0.418 MPa or less at asaturation temperature of −10° C. and is thus applicable to commerciallyavailable refrigeration apparatuses for R1234yf without significantdesign change.

When Refrigerant 4 consists of HFO-1132 (E) and HFO-1234yf, it is morepreferred that HFO-1132 (E) be present in an amount of 22.0 to 27.7 mass%, and HFO-1234yf be present in an amount of 78.0 to 72.3 mass %, basedon the total mass of HFO-1132 (E) and HFO-1234yf. In this case,Refrigerant 4 has the following characteristics: the GWP is 100 or less;it has a COP of 98% or more relative to that of R1234yf; it has arefrigerating capacity of 140% or more relative to that of R1234yf; itis slightly flammable according to ASHRAE standards (Class 2L); thedischarge temperature is 65.0° C. or less; and the critical temperatureis 83.5° C. or more. Further, in this case, Refrigerant 4 has asaturation pressure of 0.385 MPa or more and 0.417 MPa or less at asaturation temperature of −10° C., and is thus applicable tocommercially available refrigeration apparatuses for R1234yf withoutsignificant design change.

When Refrigerant 4 consists of HFO-1132 (E) and HFO-1234yf, it is evenmore preferred that HFO-1132 (E) be present in an amount of 22.5 to 27.5mass %, and HFO-1234yf be present in an amount of 77.5 to 72.5 mass %,based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case,Refrigerant 4 has the following characteristics: the GWP is 100 or less;it has a COP of 98% or more relative to that of R1234yf; it has arefrigerating capacity of 140% or more relative to that of R1234yf; itis slightly flammable according to ASHRAE standards (Class 2L); thedischarge temperature is 64.8° C. or less; and the critical temperatureis 83.8° C. or more. Further, in this case, Refrigerant 4 has asaturation pressure of 0.388 MPa or more and 0.414 MPa or less at asaturation temperature of −10° C., and is thus applicable tocommercially available refrigeration apparatuses for R1234yf withoutsignificant design change.

When Refrigerant 4 consists of HFO-1132 (E) and HFO-1234yf, it isparticularly preferred that HFO-1132 (E) be present in an amount of 23.0to 27.2 mass %, and HFO-1234yf be present in an amount of 77.0 to 72.8mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf. In thiscase, Refrigerant 4 has the following characteristics: the GWP is 100 orless; it has a COP of 98% or more relative to that of R1234yf; it has arefrigerating capacity of 141% or more relative to that of R1234yf; itis slightly flammable according to ASHRAE standards (Class 2L); thedischarge temperature is 64.8° C. or less; and the critical temperatureis 83.8° C. or more. Further, in this case, Refrigerant 4 has asaturation pressure of 0.390 MPa or more and 0.414 MPa or less at asaturation temperature of −10° C., and is thus applicable tocommercially available refrigeration apparatuses for R1234yf withoutsignificant design change.

When Refrigerant 4 consists of HFO-1132 (E) and HFO-1234yf, it isfurther particularly preferred that HFO-1132 (E) be present in an amountof 23.5 to 27.0 mass %, and HFO-1234yf be present in an amount of 76.5to 73.0 mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf.In this case, Refrigerant 4 has the following characteristics: the GWPis 100 or less; it has a COP of 98% or more relative to that of R1234yf;it has a refrigerating capacity of 142% or more relative to that ofR1234yf; it is slightly flammable according to ASHRAE standards (Class2L); the discharge temperature is 64.8° C. or less; and the criticaltemperature is 83.8° C. or more. Further, in this case, Refrigerant 4has a saturation pressure of 0.390 MPa or more and 0.414 MPa or less ata saturation temperature of −10° C., and is thus applicable tocommercially available refrigeration apparatuses for R1234yf withoutsignificant design change.

When Refrigerant 4 consists of HFO-1132 (E) and HFO-1234yf, it is mostpreferred that HFO-1132 (E) be present in an amount of 24.0 to 26.7 mass%, and HFO-1234yf be present in an amount of 76.0 to 73.3 mass %, basedon the total mass of HFO-1132 (E) and HFO-1234yf. In this case,Refrigerant 4 has the following characteristics: the GWP is 100 or less;it has a COP of 98% or more relative to that of R1234yf; it has arefrigerating capacity of 144% or more relative to that of R1234yf; itis slightly flammable according to ASHRAE standards (Class 2L); thedischarge temperature is 64.6° C. or less; and the critical temperatureis 84.0° C. or more. Further, in this case, Refrigerant 4 has asaturation pressure of 0.396 MPa or more and 0.411 MPa or less at asaturation temperature of −10° C., and is thus applicable tocommercially available refrigeration apparatuses for R1234yf withoutsignificant design change.

Refrigerant 5 according to the present disclosure is described below.

Technical Description

First, before describing Refrigerant 5, the difference between gasolinevehicles and electric vehicles, and the advantages of heat pumps, areexplained.

Difference Between Gasoline Vehicles and Electric Vehicles

Gasoline vehicles reuse engine exhaust heat to provide warm air for theheating function, whereas electric vehicles do not have a heat source tobe reused and thus use electrical power for heating. In conventional airconditioners using an electric heater, the use of the heater directlyleads to power consumption, which significantly reduces the actualdriving range. Heat pumps, which warm the interior using the temperaturedifference between a refrigerant and the outside air, achieve a heatingeffect that is higher than the power consumed, making it possible towarm the interior of a vehicle with less power than before.

Advantages of Heat Pumps

During heating, the following steps are taken: (a) a step of compressingrefrigerant gas, which is evaporated by absorbing heat from the outsidein a heat exchanger, in a compressor to form high-temperature,high-pressure gas, and (b) converting the cold air inside a vehicle intowarm air by heat exchange and blowing the warm air into the vehicle fromthe air-conditioner vents. This corresponds to the reverse cycle to acycle in which heat absorbed from the interior of a vehicle is releasedfrom an outdoor heat exchanger to provide a cooling and heating functionin the summer. Heat pumps, which can be used for both cooling andheating with one refrigerant circuit, are characterized by a highercoefficient of performance (COP) than that of heating with conventionalelectric heaters.

1.5 Refrigerant 5

In an embodiment, the refrigerant contained in the composition accordingto the present disclosure comprises HFO-1132 (E) and HFO-1234yf, whereinHFO-1132 (E) is present in an amount of 12.1 to 72.0 mass %, andHFO-1234yf is present in an amount of 87.9 to 28.0 mass %, based on thetotal mass of HFO-1132 (E) and HFO-1234yf. This refrigerant may bereferred to as “Refrigerant 5.”

In the present disclosure, Refrigerant 5 is used for an air-conditioningsystem for vehicles.

Refrigerant 5 has the above feature and thus has the followingcharacteristics: (1) the GWP is sufficiently low (100 or less); (2) ithas a COP almost equivalent to that of R1234yf; (3) it has arefrigerating capacity of 128% or more relative to that of R1234yf; and(4) the burning rate is less than 10.0 cm/s.

Refrigerant 5 comprises HFO-1132 (E) in an amount of 12.1 mass % or morebased on the total mass of HFO-1132 (E) and HFO-1234yf. This makes itpossible to ensure a boiling point of −40° C. or less, which isadvantageous when an electric vehicle is heated using a heat pump. Aboiling point of −40° C. or less means that the saturation pressure isequal to or higher than atmospheric pressure at −40° C. For the aboveapplication, a lower boiling point that is not higher than −40° C. ispreferred.

Since the boiling point of HFO-1234yf is −29° C., the saturationpressure at an evaporation temperature of −30° C. or lower is equal toor less than atmospheric pressure. Therefore, there is a problem in thatheating operation cannot be performed using a heat pump in an electricvehicle. Even if heating operation can be performed, there is a problemin that the suction pressure to the compressor is very low, whichresults in insufficient refrigeration capacity, thus taking a longperiod of time for heating. In this case, since a heat pump, which ishighly efficient for heating, cannot be used in electric vehicles, thereis a problem in that heating must be performed using an inefficientelectric heater. In contrast, with a refrigerant having a boiling pointof −40° C. or lower, heating operation can be performed using a heatpump in electric vehicles at an evaporation temperature up to −40° C.Therefore, heating operation using a heat pump can be made possible inelectric vehicles in almost every region of the world.

Refrigerant 5 comprises HFO-1132 (E) in an amount of 72.0 mass % or lessbased on the total mass of HFO-1132 (E) and HFO-1234yf. This makes itpossible to ensure a burning rate of less than 10.0 cm/s, whichcontributes to safety when used for an air-conditioning system forvehicles.

Refrigerant 5 may have a refrigerating capacity of 128% or more,preferably 130% or more, more preferably 140% or more, even morepreferably 150% or more, and particularly preferably 160% or more,relative to that of R1234yf.

Since the GWP is 5 or more and 100 or less, Refrigerant 5 can notablyreduce the burden on the environment from a global warming perspective,compared with other general-purpose refrigerants.

In Refrigerant 5, the ratio of refrigerating capacity to power consumedin a refrigeration cycle (coefficient of performance (COP)) relative tothat of R1234yf may be 100% or more from the viewpoint of energyconsumption efficiency.

The use of Refrigerant 5 for an air-conditioning system for vehiclesenables heating with a heat pump, which consumes less power thanelectric heaters.

The air-conditioning system for which Refrigerant 5 is used ispreferably for gasoline vehicles, hybrid vehicles, electric vehicles, orhydrogen vehicles. From the viewpoint of improving the travel distanceof a vehicle while the interior of the vehicle is heated with a heatpump, the air-conditioning system for which Refrigerant 5 is used isparticularly preferably for electric vehicles among these. Specifically,in the present disclosure, Refrigerant 5 is particularly preferably usedfor electric vehicles.

In the present disclosure, Refrigerant 5 is used for air-conditioningsystems for vehicles. In the present disclosure, Refrigerant 5 ispreferably used for air-conditioning systems for gasoline vehicles,air-conditioning systems for hybrid vehicles, air-conditioning systemsfor electric vehicles, or air-conditioning systems for hydrogenvehicles. In the present disclosure, Refrigerant 5 is particularlypreferably used for air-conditioning systems for electric vehicles.

In the present disclosure, Refrigerant 5 is preferably used for therefrigeration apparatus for vehicles, such as gasoline vehicles, hybridvehicles, plug-in hybrid vehicles, electric vehicles, hydrogen vehicles,and fuel cell vehicles. Of these, Refrigerant 5 is particularlypreferably used for the refrigeration apparatus for electric vehicles,in which engine exhaust heat cannot be used.

Further, in a situation in which the engine exhaust heat cannot be useddue to, for example, defects in the thermostat when the engine starts,the use of heat pump heating with Refrigerant 5 can immediately warm theinside of vehicles even when the vehicles are gasoline vehicles, hybridvehicles, plug-in hybrid vehicles, hydrogen vehicles, and fuel cellvehicles.

In the present disclosure, Refrigerant 5 has a boiling point ofpreferably-51.2 to −40.0° C., more preferably-50.0 to −42.0° C., andeven more preferably-48.0 to −44.0° C., since a pressure equal to orhigher than atmospheric pressure at −40° C. is required when theinterior of a vehicle is heated using a heat pump.

In Refrigerant 5, it is preferred that HFO-1132 (E) be present in anamount of 15.0 to 65.0 mass %, and HFO-1234yf be present in an amount of85.0 to 35.0 mass %, based on the total mass of HFO-1132 (E) andHFO-1234yf.

In Refrigerant 5, it is more preferred that HFO-1132 (E) be present inan amount of 20.0 to 55.0 mass %, and HFO-1234yf be present in an amountof 80.0 to 45.0 mass %, based on the total mass of HFO-1132 (E) andHFO-1234yf.

In Refrigerant 5, it is even more preferred that HFO-1132 (E) be presentin an amount of 25.0 to 50.0 mass %, and HFO-1234yf be present in anamount of 75.0 to 50.0 mass %, based on the total mass of HFO-1132 (E)and HFO-1234yf.

In Refrigerant 5, it is particularly preferred that HFO-1132 (E) bepresent in an amount of 30.0 to 45.0 mass %, and HFO-1234yf be presentin an amount of 70.0 to 55.0 mass %, based on the total mass of HFO-1132(E) and HFO-1234yf.

In Refrigerant 5, it is most preferred that HFO-1132 (E) be present inan amount of 35.0 to 40.0 mass %, and HFO-1234yf be present in an amountof 65.0 to 60.0 mass %, based on the total mass of HFO-1132 (E) andHFO-1234yf.

In the present disclosure, the burning rate of Refrigerant 5 ispreferably less than 10.0 cm/s, more preferably less than 5.0 cm/s, evenmore preferably less than 3.0 cm/s, and particularly preferably lessthan 2.0 cm/s.

In the present disclosure, Refrigerant 5 is preferably used foroperating a refrigeration cycle in which the evaporation temperature is−40 to 10° C. from the viewpoint of obtaining a refrigerating capacityequivalent to or higher than that of R1234yf.

In the present disclosure, when Refrigerant 5 is used for operating arefrigeration cycle, the discharge temperature is preferably 79° C. orless, more preferably 75° C. or less, even more preferably 70° C. orless, and particularly preferably 67° C. or less.

Refrigerant 5 may comprise HFO-1132 (E) and HFO-1234yf in such amountsthat the sum of their concentrations is usually 99.5 mass % or more. Inthe present disclosure, the total amount of HFO-1132 (E) and HFO-1234yfis preferably 99.7 mass % or more, more preferably 99.8 mass % or more,and even more preferably 99.9 mass % or more, of entire Refrigerant 5.

Refrigerant 5 may further comprise an additional refrigerant in additionto HFO-1132 (E) and HFO-1234yf as long as the above characteristics arenot impaired. In this case, the content of the additional refrigerant ispreferably 0.5 mass % or less, more preferably 0.3 mass % or less, evenmore preferably 0.2 mass % or less, and particularly preferably 0.1 mass% or less, of entire Refrigerant 5. The additional refrigerant is notlimited and may be selected from a wide range of known refrigerantswidely used in the field. Refrigerant 5 may comprise one additionalrefrigerant or two or more additional refrigerants.

It is particularly preferred that Refrigerant 5 consist of HFO-1132 (E)and HFO-1234yf. In other words, the total concentration of HFO-1132 (E)and HFO-1234yf in Refrigerant 5 is particularly preferably 100 mass % ofentire Refrigerant 5.

When Refrigerant 5 consists of HFO-1132 (E) and HFO-1234yf, HFO-1132 (E)is usually present in an amount of 12.1 to 72.0 mass %, and HFO-1234yfis usually present in an amount of 87.9 to 28.0 mass %, based on thetotal mass of HFO-1132 (E) and HFO-1234yf.

When Refrigerant 5 consists of HFO-1132 (E) and HFO-1234yf, it ispreferred that HFO-1132 (E) be present in an amount of 15.0 to 65.0 mass%, and HFO-1234yf be present in an amount of 85.0 to 35.0 mass %, basedon the total mass of HFO-1132 (E) and HFO-1234yf.

When Refrigerant 5 consists of HFO-1132 (E) and HFO-1234yf, it is morepreferred that HFO-1132 (E) be present in an amount of 20.0 to 55.0 mass%, and HFO-1234yf be present in an amount of 80.0 to 45.0 mass %, basedon the total mass of HFO-1132 (E) and HFO-1234yf.

When Refrigerant 5 consists of HFO-1132 (E) and HFO-1234yf, it is evenmore preferred that HFO-1132 (E) be present in an amount of 25.0 to 50.0mass %, and HFO-1234yf be present in an amount of 75.0 to 50.0 mass %,based on the total mass of HFO-1132 (E) and HFO-1234yf.

When Refrigerant 5 consists of HFO-1132 (E) and HFO-1234yf, it isparticularly preferred that HFO-1132 (E) be present in an amount of 30.0to 45.0 mass %, and HFO-1234yf be present in an amount of 70.0 to 55.0mass %, based on the total mass of HFO-1132 (E) and HFO-1234yf.

When Refrigerant 5 consists of HFO-1132 (E) and HFO-1234yf, it is mostpreferred that HFO-1132 (E) be present in an amount of 35.0 to 40.0 mass%, and HFO-1234yf be present in an amount of 65.0 to 60.0 mass %, basedon the total mass of HFO-1132 (E) and HFO-1234yf.

1.6 Application

The composition containing the refrigerant according to the presentdisclosure can be widely used as a working fluid for known refrigerantapplications in 1) a refrigeration method comprising operating arefrigeration cycle and 2) a method for operating a refrigerationapparatus that operates a refrigeration cycle.

The refrigeration cycle herein means performing energy conversion bycirculating in the refrigeration apparatus the refrigerant (Refrigerant1, 2, 3, 4, or 5 according to the present disclosure) in the state ofthe single refrigerant, or in the state of a refrigerant composition ora refrigerant-oil-containing working fluid explained below, through acompressor.

The composition containing the refrigerant according to the presentdisclosure is not limited; however, it is suitably used in avapor-compression refrigeration cycle. A vapor-compression refrigerationcycle comprises a series of cycles of (1) compressing a refrigerant in agaseous state in a compressor, (2) cooling the refrigerant to convert itinto a high-pressure liquid state in a condenser, (3) reducing thepressure with an expansion valve, and (4) evaporating the liquidrefrigerant at a low temperature in an evaporator and removing heat bythe heat of evaporation. Depending on the system of compressing gaseousrefrigerants, vapor-compression refrigeration cycles can be classifiedinto a turbo (centrifugal) cycle, a reciprocating cycle, a twin-screwcycle, a single-screw cycle, a scroll compressor cycle, etc., and can beselected according to heat capacity, compression ratio, and size.

The composition containing the refrigerant according to the presentdisclosure is not limited, and is suitable as a refrigerant used forlarge chiller refrigerators, and particularly turbo (centrifugal)compressors.

The present disclosure includes use of the refrigerant (or compositioncomprising the refrigerant) according to the present disclosure in arefrigeration method, use of the refrigerant (or composition comprisingthe refrigerant) according to the present disclosure in a method ofoperating a refrigeration apparatus etc., and a refrigeration apparatusor the like comprising the refrigerant (or composition comprising therefrigerant) according to the present disclosure.

The composition comprising Refrigerant 1 according to the presentdisclosure is used for operating a refrigeration cycle in which theevaporation temperature is −75 to −5° C.

By using the composition comprising Refrigerant 1 according to thepresent disclosure for operating a refrigeration cycle in which theevaporation temperature is −75 to −5° C., there is an advantage that arefrigerating capacity that is equivalent to or higher than that ofR404A can be obtained. In the refrigeration cycle in which thecomposition comprising Refrigerant 1 according to the present disclosureis used, the evaporation temperature is preferably −65° C. to −5° C.,more preferably −60° C. to −7.5° C., even more preferably −55° C. to−10° C., and particularly preferably −50° C. to −35° C.

In the refrigeration cycle in which the composition comprisingRefrigerant 1 according to the present disclosure is used, theevaporation temperature is preferably −7.5° C. or less, more preferably−10° C. or less, even more preferably −35° C. or less.

In the refrigeration cycle in which the composition comprisingRefrigerant 1 according to the present disclosure is used, theevaporation temperature is preferably −65° C. or more, more preferably−60° C. or more, even more preferably −55° C. or more, and particularlypreferably −50° C. or more.

From the viewpoint of obtaining a refrigerating capacity that isequivalent to or higher than R404A, the composition comprisingRefrigerant 2 according to the present disclosure is preferably used foroperating a refrigeration cycle in which the evaporation temperature is−75 to 15° C. In the refrigeration cycle in which the compositioncomprising Refrigerant 2 according to the present disclosure is used,the evaporation temperature is preferably −65° C. to 10° C., morepreferably −60° C. to 5° C., even more preferably −55° C. to 0° C., andparticularly preferably −50° C. to −5° C.

In the refrigeration cycle in which the composition comprisingRefrigerant 2 according to the present disclosure is used, theevaporation temperature is preferably 15° C. or less, more preferably 5°C. or less, even more preferably 0° C. or less, and particularlypreferably −5° C. or less.

In the refrigeration cycle in which the composition comprisingRefrigerant 2 according to the present disclosure is used, theevaporation temperature is preferably −65° C. or more, more preferably−60° C. or more, even more preferably −55° C. or more, and particularlypreferably −50° C. or more.

From the viewpoint of obtaining a refrigerating capacity that isequivalent to or higher than R134a, the composition comprisingRefrigerant 3 according to the present disclosure is preferably used foroperating a refrigeration cycle in which the evaporation temperature is−75 to 15° C. In the refrigeration cycle in which the compositioncomprising Refrigerant 3 according to the present disclosure is used,the evaporation temperature is preferably −65° C. to 15° C., morepreferably −60° C. to 5° C., even more preferably −55° C. to 0° C., andparticularly preferably −50° C. to −5° C.

In the refrigeration cycle in which the composition comprisingRefrigerant 3 according to the present disclosure is used, theevaporation temperature is preferably 15° C. or less, more preferably 5°C. or less, even more preferably 0° C. or less, and particularlypreferably −5° C. or less.

In the refrigeration cycle in which the composition comprisingRefrigerant 3 according to the present disclosure is used, theevaporation temperature is preferably −65° C. or more, more preferably−60° C. or more, even more preferably −55° C. or more, and particularlypreferably −50° C. or more.

In the refrigeration cycle in which the composition comprisingRefrigerant 3 according to the present disclosure is used, theevaporation temperature is preferably −65° C. or more to 15° C. or less,more preferably −60° C. or more to 5° C. or less, even more preferably−55° C. or more to 0° C. or less, and particularly preferably −50° C. ormore to −5° C. or less.

From the viewpoint of obtaining a refrigerating capacity of 140% or morerelative to that of R1234yf, the composition comprising Refrigerant 4according to the present disclosure is preferably used for operating arefrigeration cycle in which the evaporation temperature is −75 to 20°C. In the refrigeration cycle in which the composition comprisingRefrigerant 4 according to the present disclosure is used, theevaporation temperature is preferably −65° C. to 15° C., more preferably−60° C. to 10° C., even more preferably −55° C. to 7.5° C., andparticularly preferably −50° C. to 5° C.

From the viewpoint of obtaining a refrigerating capacity of 140% or morerelative to that of R1234yf, in the refrigeration cycle in which thecomposition comprising Refrigerant 4 according to the present disclosureis used, the evaporation temperature is preferably 20° C. or less, morepreferably 15° C. or less, even more preferably 10° C. or less, andparticularly preferably 5° C. or less.

From the viewpoint of obtaining a refrigerating capacity of 140% or morerelative to that of R1234yf, in the refrigeration cycle in which hecomposition comprising Refrigerant 4 according to the present disclosureis used, the evaporation temperature is preferably −75° C. or more, morepreferably −60° C. or more, even more preferably −55° C. or more, andparticularly preferably −50° C. or more.

Preferable examples of refrigeration apparatuses in which Refrigerant 1,2, 3, or 4 (or a composition containing the refrigerant) according tothe present disclosure can be used include air-conditioning systems,refrigerators, freezers, water coolers, ice makers, refrigeratedshowcases, freezing showcases, freezing and refrigerating units,refrigerating machines for freezing and refrigerating warehouses,air-conditioning systems for vehicles, turbo refrigerating machines, orscrew refrigerating machines. Of these, air-conditioning systems forvehicles are preferred. Of the air-conditioning systems for vehicles,air-conditioning systems for gas vehicles, air-conditioning systems forhybrid vehicles, air-conditioning systems for electric vehicles, andair-conditioning systems for hydrogen vehicles are more preferred. Ofthe air-conditioning systems for vehicles, air-conditioning systems forelectric vehicles are particularly preferred.

The composition comprising Refrigerant 1 or 2 according to the presentdisclosure is suitably used as an alternative refrigerant for R12, R22,R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A,R422B, R422C, R422D, R423A, R424A, R426A, R427A, R430A, R434A, R437A,R438A, R448A, R449A, R449B, R449C, R452A, R452B, R454A, R454B, R454C,R455A, R465A, R502, R507, or R513A. The composition comprisingRefrigerant 1 or 2 according to the present disclosure is suitably usedas an alternative refrigerant for R22, R404A, R407F, R407H, R448A,R449A, R454C, R455A, or R465A. Additionally, since the compositioncomprising Refrigerant 1 or 2 according to the present disclosure has arefrigerating capacity equivalent to R404A, which has been widely used,and a sufficiently low GWP, it is particularly suitable as analternative refrigerant for R404A.

The composition comprising Refrigerant 3 according to the presentdisclosure is suitably used as an alternative refrigerant for R134a,R1234yf, or CO₂. The composition comprising Refrigerant 3 according tothe present disclosure is suitably used as an alternative refrigerantfor R134a. Additionally, since the composition comprising Refrigerant 3according to the present disclosure has a refrigerating capacity of 150%or more relative to that of R134a, which has been widely used, and asufficiently low GWP, it is particularly suitable as an alternativerefrigerant for R134a.

The composition comprising Refrigerant 4 according to the presentdisclosure is suitably used as an alternative refrigerant for R12, R22,R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A,R422B, R422C, R422D, R423A, R424A, R426A, R427A, R430A, R434A, R437A,R438A, R448A, R449A, R449B, R449C, R452A, R452B, R454A, R454B, R454C,R455A, R465A, R502, R507, R513A, R1234yf, or R1234ze. The compositioncomprising Refrigerant 4 according to the present disclosure is suitablyused as an alternative refrigerant for R12, R134a, R404A, R407C, R449C,R454C, R1234yf, or R1234ze. Additionally, since the compositioncomprising Refrigerant 4 according to the present disclosure has arefrigerating capacity of 140% or more relative to that of R1234yf,which has been widely used, and a sufficiently low GWP, it isparticularly suitable as an alternative refrigerant for R1234yf.

The composition comprising Refrigerant 5 according to the presentdisclosure is suitably used as an alternative refrigerant for R12, R22,R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A,R422B, R422C, R422D, R423A, R424A, R426A, R427A, R430A, R434A, R437A,R438A, R448A, R449A, R449B, R449C, R452A, R452B, R454A, R454B, R454C,R455A, R465A, R502, R507, R513A, R1234yf, or R1234ze. The compositioncomprising Refrigerant 5 according to the present disclosure is suitablyused as an alternative refrigerant for R12, R134a, or R1234yf.Additionally, since the composition comprising Refrigerant 5 accordingto the present disclosure has a refrigerating capacity of 140% or morerelative to that of R1234yf, which has been widely used, and asufficiently low GWP, it is particularly suitable as an alternativerefrigerant for R1234yf.

The composition comprising Refrigerant 5 according to the presentdisclosure is preferably used in air-conditioning systems for vehicles.The air-conditioning systems for vehicles are preferablyair-conditioning systems for gas vehicles, air-conditioning systems forhybrid vehicles, air-conditioning systems for electric vehicles, orair-conditioning systems for hydrogen vehicles. Of these, theair-conditioning systems for vehicles are particularly preferablyair-conditioning systems for electric vehicles. That is, in the presentdisclosure, the composition comprising Refrigerant 5 is particularlypreferably used for electric vehicles.

2. Refrigerant Composition

The refrigerant composition of the present invention at least includesthe refrigerant according to the present disclosure and can be used forthe same applications as the refrigerant of the present disclosure.

Further, the refrigerant composition according to the present disclosureis mixed with at least a refrigerant oil. The refrigerant compositioncan thereby be used for obtaining a working fluid for a refrigerationapparatus.

The refrigerant composition according to the present disclosure furthercomprises at least one other component in addition to the refrigerant ofthe present disclosure. The refrigerant composition according to thepresent disclosure may optionally comprise at least one of the othercomponents describes below.

As described above, when the refrigerant composition according to thepresent disclosure is used as a working fluid for a refrigerationapparatus, it is usually mixed with at least a refrigerant oil for use.

Preferably, the refrigerant composition according to the presentdisclosure is substantially free from refrigerant oil. Specifically, inthe refrigerant composition according to the present disclosure, theamount of refrigerant oil relative to the entire refrigerant compositionis preferably 0 to 1 mass %, more preferably 0 to 0.5 mass %, even morepreferably 0 to 0.25 mass %, and particularly preferably 0 to 0.1 mass%.

2.1 Water

The refrigerant composition according to the present disclosure maycomprise a small amount of water.

The water content in the refrigerant composition is preferably 0 to 0.1mass %, more preferably 0 to 0.075 mass %, even more preferably 0 to0.05 mass %, and particularly preferably 0 to 0.025 mass % relative tothe entire refrigerant.

A small amount of water contained in the refrigerant compositionstabilizes double bonds in the molecules of unsaturatedfluorocarbon-based compounds that can be present in the refrigerant; andmakes it less likely that the unsaturated fluorocarbon-based compoundswill be oxidized, thus increasing the stability of the refrigerantcomposition. To attain the above effects that are obtained by containingwater, the lower limit of the water content is about 0.001 mass %. Forexample, the water content can be adjusted in a range of 0.001 to 0.1mass %, 0.001 to 0.075 mass %, 0001 to 0.05 mass %, and 0.001 to 0.025mass %.

2.2 Tracer

A tracer is added to the refrigerant composition according to thepresent disclosure at a detectable concentration so that when thecomposition has been diluted, contaminated, or undergone some otherchanges, the tracer can trace the changes.

The refrigerant composition according to the present disclosure maycomprise a single tracer, or two or more tracers.

The tracer is not limited, and can be suitably selected from typicallyused tracers. Preferably, a compound that cannot become an impurityinevitably mixed into the refrigerant of the present disclosure can beselected as a tracer.

Examples of tracers include hydrofluorocarbons,hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons,fluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons,perfluorocarbons, fluoroethers, brominated compounds, iodinatedcompounds, alcohols, aldehydes, ketones, and nitrous oxides (N₂O). Ofthese, hydrofluorocarbons, hydrochlorofluorocarbons,chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, and fluoroethersare preferred.

Specifically, the following compounds (hereinbelow sometimes referred toas “tracer compounds”) are more preferred as tracers.

HCC-40 (chloromethane, CH₃Cl), HFC-41 (fluoromethane, CH₃F), HFC-161(fluoroethane, CH₃CH₂F), HFC-245fa (1,1,1,3,3-pentafluoropropane,CF₃CH₂CHF₂), HFC-236fa (1,1,1,3,3,3-hexafluoropropane, CF₃CH₂CF₃),HFC-236ea (1,1,1,2,3,3-hexafluoropropane, CF₃CHFCHF₂), HCFC-22(chlorodifluoromethane, CHClF₂), HCFC-31 (chlorofluoromethane, CH₂ClF),CFC-1113 (chlorotrifluoroethylene, CF₂═CClF), HFE-125 (trifluoromethyldifluoro methyl ether, CF₃OCHF₂), HFE-134a (trifluoromethyl fluoromethylether, CF₃OCH₂F), HFE-143a (trifluoromethyl methyl ether, CF₃OCH₃),HFE-227ea (trifluoromethyl tetrafluoro ethyl ether, CF₃OCHFCF₃), andHFE-236fa (trifluoromethyl trifluoroethyl ether, CF₃OCH₂CF₃).

The tracer compound can be present in the refrigerant composition in atotal concentration of 10 to 1000 ppm. The tracer compound is preferablypresent in the refrigerant composition in a total concentration of 30 to500 ppm, more preferably 50 to 300 ppm, even more preferably 75 to 250ppm, and particularly preferably 100 to 200 ppm.

2.3 Ultraviolet Fluorescent Dye

The refrigerant composition according to the present disclosure maycomprise a single ultraviolet fluorescent dye, or two or moreultraviolet fluorescent dyes.

The ultraviolet fluorescent dye is not limited, and can be suitablyselected from typically used ultraviolet fluorescent dyes.

Examples of ultraviolet fluorescent dyes include naphthalimide,coumarin, anthracene, phenanthrene, xanthene, thioxanthene,naphthoxanthene, fluorescein, and derivatives thereof. Of these,naphthalimide and coumarin are preferred.

The amount of the ultraviolet fluorescent dye is not limited, and isusually 0.01 to 5 mass %, preferably 0.05 to 3 mass %, more preferably0.1 to 2 mass %, even more preferably 0.25 to 1.5 mass %, andparticularly preferably 0.5 to 1 mass %, relative to the entirerefrigerant.

2.4 Stabilizer

The refrigerant composition according to the present disclosure maycomprise a single stabilizer, or two or more stabilizers.

The stabilizer is not limited, and can be suitably selected fromtypically used stabilizers.

Examples of stabilizers include nitro compounds, ethers, and amines.

Examples of nitro compounds include aliphatic nitro compounds, such asnitromethane and nitroethane, and aromatic nitro compounds, such asnitro benzene and nitro styrene.

Examples of ethers include 1,4-dioxane.

Examples of amines include 2,2,3,3,3-pentafluoropropylamine and diphenylamine.

Examples of stabilizers also include butylhydroxyxylene andbenzotriazole in addition to nitro compounds, ethers, and amines.

The amount of the stabilizer is not limited. The amount of thestabilizer is usually 0.01 to 5 mass %, preferably 0.05 to 3 mass %,more preferably 0.1 to 2 mass %, even more preferably 0.25 to 1.5 mass%, and particularly preferably 0.5 to 1 mass %, relative to the entirerefrigerant.

The stability of the refrigerant composition according to the presentdisclosure can be evaluated by a commonly used method withoutlimitation. Examples of such methods include an evaluation method usingthe amount of free fluorine ions as an index according to ASHRAEStandard 97-2007, and the like. There is, for example, anotherevaluation method using the total acid number as an index. This methodcan be performed, for example, according to ASTM D 974-06.

2.5 Polymerization Inhibitor

The refrigerant composition according to the present disclosure maycomprise a single polymerization inhibitor, or two or morepolymerization inhibitors.

The polymerization inhibitor is not limited, and can be suitablyselected from typically used polymerization inhibitors.

Examples of polymerization inhibitors include 4-methoxy-1-naphthol,hydroquinone, hydroquinone methyl ether, dimethyl-t-butylphenol,2,6-di-tert-butyl-p-cresol, and benzotriazole.

The amount of the polymerization inhibitor is not limited. The amount ofthe polymerization inhibitor is usually 0.01 to 5 mass %, preferably0.05 to 3 mass %, more preferably 0.1 to 2 mass %, even more preferably0.25 to 1.5 mass %, and particularly preferably 0.5 to 1 mass %,relative to the entire refrigerant.

2.6 Other Components that can be Contained in Refrigerant Composition

The refrigerant composition according to the present disclosure can alsocontain the following components.

For example, fluorinated hydrocarbons that are different from therefrigerants mentioned above can be contained. Examples of fluorinatedhydrocarbons used as other components are not limited. At least onefluorinated hydrocarbon selected from the group consisting of HCFC-1122,HCFC-124, and CFC-1113 can be used.

As another component, at least one halogenated organic compoundrepresented by formula (A): CmHnXp, wherein each X is independentlyfluorine, chlorine, or bromine; m is 1 or 2; 2m+2 is greater than orequal to n+p; and p is greater than or equal to 1 can be contained. Thehalogenated organic compound is not limited, and preferable examplesinclude difluorochloromethane, chloromethane,2-chloro-1,1,1,2,2-pentafluoroethane,2-chloro-1,1,1,2-tetrafluoroethane, 2-chloro-1,1-difluoroethylene, andtrifluoroethylene.

As another component, at least one organic compound represented byformula (B): CmHnXp, wherein each X is independently an atom other thana halogen atom; m is 1 or 2; 2m+2 is greater than or equal to n+p; and pis greater than or equal to 1 can be contained. The organic compound isnot limited, and preferable examples include propane and isobutane.

The amounts of the fluorinated hydrocarbon, halogenated organic compoundrepresented by formula (A), and organic compound represented by formula(B) are not limited. The total amount of these is preferably 0.5 mass %or less, more preferably 0.3 mass % or less, and particularly preferably0.1 mass % or less, relative to the total amount of the refrigerantcomposition.

3. Refrigerant-Oil-Containing Working Fluid

The refrigerant-oil-containing working fluid according to the presentdisclosure at least includes the refrigerant or the refrigerantcomposition according to the present disclosure, and a refrigerant oil,and is used as a working fluid in a refrigeration apparatus.Specifically, the refrigerant-oil-containing working fluid according tothe present disclosure can be obtained by mixing together therefrigerant or refrigerant composition with a refrigerant oil used in acompressor of a refrigeration apparatus.

The amount of the refrigerant oil is not limited, and is usually 10 to50 mass %, preferably 12.5 to 45 mass %, more preferably 15 to 40 mass%, even more preferably 17.5 to 35 mass %, and particularly preferably20 to 30 mass %, relative to the entire refrigerant-oil-containingworking fluid.

3.1 Refrigerant Oil

The composition according to the present disclosure may comprise asingle refrigerant oil or two or more refrigerant oils.

The refrigerant oil is not limited, and can be suitably selected fromtypically used refrigerant oils. In this case, refrigerant oils that aresuperior in increasing action on the miscibility with the mixture of therefrigerant according to the present disclosure (mixed refrigerantaccording to the present disclosure) and stability of the mixedrefrigerant, for example, are suitably selected as necessary.

The base oil of the refrigerant oil is preferably, for example, at leastone member selected from the group consisting of polyalkylene glycols(PAG), polyol esters (POE), and polyvinyl ethers (PVE).

The refrigerant oil may further comprise an additive in addition to thebase oil.

The additive may be at least one member selected from the groupconsisting of antioxidants, extreme-pressure agents, acid scavengers,oxygen scavengers, copper deactivators, anticorrosive agents, oilyagents, and antifoaming agents.

A refrigerant oil with a kinematic viscosity of 5 to 400 cSt at 40° C.is preferable from the standpoint of lubrication.

The refrigerant-oil-containing working fluid according to the presentdisclosure may further optionally comprise at least one additive.Examples of additives include compatibilizing agents described below.

3.2 Compatibilizing Agent

The refrigerant-oil-containing working fluid according to the presentdisclosure may comprise a single compatibilizing agent or two or morecompatibilizing agents.

The compatibilizing agent is not limited, and can be suitably selectedfrom typically used compatibilizing agents.

Examples of compatibilizing agents include polyoxyalkylene glycolethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, arylethers, fluoroethers, and 1,1,1-trifluoroalkane. Of these, apolyoxyalkylene glycol ether is preferred.

EXAMPLES

More specific explanation is given below with reference to Examples.However, the present disclosure is not limited to the followingExamples.

Test Example 1-1

The GWP of each mixed refrigerant shown in Examples 1-1 to 1-13,Comparative Examples 1-1 to 1-2, and Reference Example 1-1 (R404A) wasevaluated based on the values in the IPCC fourth report.

The COP, refrigerating capacity, discharge temperature, saturationpressure at a saturation temperature of 40° C., condensation pressure,and evaporation pressure of each of the mixed refrigerants weredetermined by performing refrigeration cycle theoretical calculationsfor the mixed refrigerants by using the National Institute of Scienceand Technology (NIST) and Reference Fluid Thermodynamic and TransportProperties Database (Refprop 10.0) under the following conditions.

Evaporation temperature: −50° C.

Condensation temperature: 40° C.

Superheating temperature: 20 K

Supercooling temperature: 0 K

Compressor efficiency: 70%

The “evaporation temperature of −50° C.” means that the evaporationtemperature of the mixed refrigerant in the evaporator provided in therefrigeration apparatus is −50° C. Further, the “condensationtemperature of 40° C.” means that the condensation temperature of themixed refrigerant in the condenser provided in the refrigerationapparatus is 40° C.

Table 1 shows the results of Test Example 1-1. Table 1 shows Examplesand Comparative Examples with regard to a Refrigerant 1 of the presentdisclosure. In Table 1, the “COP ratio” and the “refrigerating capacityratio” refer to a ratio (%) relative to R404A. In Table 1, the“saturation pressure (40° C.)” refers to a saturation pressure at asaturation temperature of 40° C. In Table 1, the “discharge temperature(° C.)” refers to a temperature at which the refrigerant has the highesttemperature in the refrigeration cycle according to the refrigerationcycle theoretical calculations of the mixed refrigerant.

The coefficient of performance (COP) was calculated according to thefollowing equation.COP=(refrigerating capacity or heating capacity)/amount of electricalpower consumed

The compression ratio was calculated according to the followingequation.Compression ratio=condensation pressure(Mpa)/evaporation pressure(Mpa)

The flammability of the mixed refrigerant was determined by specifyingthe fractionation of the mixed refrigerant to the WCF concentration andmeasuring the burning rate according to ANSI/ASHRAE Standard 34-2013.The one with a burning rate of 0 cm/s to 10 cm/s was classified as Class2L (slightly flammable), the one with a burning rate of more than 10cm/s was classified as Class 2 (weakly flammable), and the one with noflame propagation was classified as Class 1 (non-flammable). In Table 1,the ASHRAE flammability classification shows the results based on thesecriteria.

The burning rate test was performed as follows. First, a mixedrefrigerant having a purity of 99.5% or more was used, and the mixedrefrigerant was deaerated by repeating a cycle of freezing, pumping, andthawing until no trace of air was observed on the vacuum gauge. Theburning rate was measured by a closed method. The initial temperaturewas the ambient temperature. The ignition was performed by generating anelectrical spark between the electrodes in the center of the samplecell. The duration of the discharge was 1.0 to 9.9 ms, and the ignitionenergy was typically about 0.1 to 1.0 J. The spread of the flame wasvisualized by using a schlieren photograph. A cylindrical container(inner diameter: 155 mm, length: 198 mm) having two acrylic windows thattransmit light was used as a sample cell, and a xenon lamp was used as alight source. The schlieren image of the flame was recorded using ahigh-speed digital video camera at a frame speed of 600 fps, and storedin a PC.

The flammable range of the mixed refrigerant was measured using ameasurement device according to ASTM E681-09 (see FIG. 1 ).

More specifically, a 12-L spherical glass flask was used so that thecombustion state could be visually observed and photographicallyrecorded. When excessive pressure was generated by combustion in theglass flask, gas was allowed to escape from the upper lid. Ignition wasachieved by electric discharge from electrodes disposed at one-third thedistance from the bottom.

Test Conditions

Test vessel: 280-mm ϕ spherical (internal volume: 12 liters)

Test temperature: 60° C.±3° C.

Pressure: 101.3 kPa±0.7 kPa

Water: 0.0088 g±0.0005 g (water content at a relative humidity of 50% at23° C.) per gram of dry air

Mixing ratio of refrigerant composition/air: 1 vol. % increments±0.2vol. %

Mixture of refrigerant composition: ±0.1 mass %

Ignition method: AC discharge, voltage: 15 kV, electric current: 30 mA,neon transformer

Electrode spacing: 6.4 mm (¼ inch)

Spark: 0.4 seconds±0.05 seconds

Evaluation Criteria:

When the flame spread at an angle of more than 90° from the ignitionpoint, it was evaluated that flame propagation was present (flammable).

When the flame spread at an angle of 90° or less from the ignitionpoint, it was evaluated that flame propagation was absent(non-flammable).

TABLE 1 Reference Comparative Example 1-1 Example Example ExampleExample Example Example Example Item Unit (R404A) 1-1 1-1 1-2 1-3 1-41-5 1-6 Composition HFO-1132 (E) mass % 0 30.0 40.0 40.5 41.3 43.0 45.047.0 ratio HFO-1234yf mass % 0 70.0 60.0 59.5 58.7 57.0 55.0 53.0HFC-134a mass % 40 0 0 0 0 0 0 0 HFC-143a mass % 52.0 0 0 0 0 0 0 0HFC-125 mass % 44.0 0 0 0 0 0 0 0 GWP (AR4) — 3922 6 6 6 6 7 7 7Discharge temperature ° C. 100.6 108.6 114.7 115.0 115.5 116.5 117.6118.8 Saturation pressure MPa 1.822 1.592 1.745 1.752 1.764 1.788 1.8171.844 (40° C.) Evaporation pressure MPa 0.082 0.063 0.072 0.073 0.0740.075 0.077 0.079 Compression ratio — 22.2 25.3 24.1 24.0 23.9 23.8 23.623.4 COP ratio (relative to % 100 106.2 106.2 106.2 106.2 106.2 106.2106.2 R404A) Refrigerating capacity % 100 86.2 98.5 99.1 100 102.1 104.5106.9 ratio (relative to R404A) ASHRAE flammability — Class 1 Class 2LClass 2L Class 2L Class 2L Class 2L Class 2L Class 2L classificationComparative Example Example Example Example Example Example ExampleExample Item 1-7 1-8 1-9 1-10 1-11 1-12 1-13 1-2 Composition HFO-1132(E) 49.2 51.0 53.5 55.0 57.0 59.0 60.0 70.0 ratio HFO-1234yf 50.8 49.046.5 45.0 43.0 41.0 40.0 30.0 HFC-134a 0 0 0 0 0 0 0 0 HFC-143a 0 0 0 00 0 0 0 HFC-125 0 0 0 0 0 0 0 0 GWP (AR4) 7 7 7 7 7 8 8 8 Dischargetemperature 120.0 121.0 122.4 123.3 124.4 125.5 126.0 131.7 Saturationpressure 1.874 1.898 1.931 1.950 1.975 2.000 2.012 2.128 (40° C.)Evaporation pressure 0.081 0.083 0.085 0.086 0.088 0.090 0.091 0.099Compression ratio 23.1 23.0 22.8 22.6 22.5 22.3 22.2 21.6 COP ratio(relative to 106.2 106.3 106.3 106.3 106.3 106.4 106.4 106.7 R404A)Refrigerating capacity 109.5 111.7 114.6 116.4 118.7 121 122.2 133.3ratio (relative to R404A) ASHRAE flammability Class 2L Class 2L Class 2LClass 2 Class 2 Class 2 Class 2 Class 2 classification

Test Example 1-2

The GWP of each mixed refrigerant shown in Examples 1-14 to 1-26,Comparative Examples 1-3 to 1-4, and Reference Example 1-2 (R404A) wasevaluated based on the values in the IPCC fourth report.

The COP, refrigerating capacity, discharge temperature, saturationpressure at a saturation temperature of 40° C., condensation pressure,and evaporation pressure of each of the mixed refrigerants weredetermined by performing refrigeration cycle theoretical calculationsfor the mixed refrigerants by using NIST and Refprop 10.0 under thefollowing conditions.

Evaporation temperature: −35° C.

Condensation temperature: 40° C.

Superheating temperature: 20 K

Supercooling temperature: 0 K

Compressor efficiency: 70%

The definitions of the terms are the same as those in Test Example 1-1.

Table 2 shows the results of Test Example 1-2. Table 2 shows Examplesand Comparative Examples with regard to a Refrigerant 1 of the presentdisclosure. In Table 2, the definitions of the terms are the same asthose in Test Example 1-1.

The coefficient of performance (COP) and the compression ratio weredetermined as in Test Example 1-1.

The flammability of the mixed refrigerant was evaluated as in TestExample 1-1. The burning rate test was performed as in Test Example 1-1.

The flammable range of the mixed refrigerant was measured in the samemanner and under the same conditions as in Test Example 1-1 by using ameasurement device according to ASTM E681-09 (see FIG. 1 ).

TABLE 2 Reference Comparative Example 1-2 Example Example ExampleExample Example Example Example Item Unit (R404A) 1-3 1-14 1-15 1-161-17 1-18 1-19 Composition HFO-1132 (E) mass % 0 30.0 40.0 40.5 41.343.0 45.0 47.0 ratio HFO-1234yf mass % 0 70.0 60.0 59.5 58.7 57.0 55.053.0 HFC-134a mass % 4.0 0 0 0 0 0 0 0 HFC-143a mass % 52.0 0 0 0 0 0 00 HFC-125 mass % 44.0 0 0 0 0 0 0 0 GWP (AR4) — 3922 6 6 6 6 7 7 7Discharge temperature ° C. 89.1 95.8 100.6 100.8 101.2 102.0 102.9 103.8Saturation pressure MPa 1.822 1.592 1.745 1.752 1.764 1.788 1.817 1.844(40° C.) Evaporation pressure MPa 0.165 0.131 0.148 0.149 0.151 0.1540.157 0.160 Compression ratio — 11.0 12.2 11.8 11.7 11.7 11.6 11.6 11.5COP ratio (relative to % 100 105.1 104.8 104.7 104.7 104.7 104.6 104.5R404A) Refrigerating capacity % 100 87.7 98.5 99.0 99.8 101.6 103.7105.7 ratio (relative to R404A) ASHRAE flammability — Class 1 Class 2LClass 2L Class 2L Class 2L Class 2L Class 2L Class 2L classificationComparative Example Example Example Example Example Example ExampleExample Item 1-20 1-21 1-22 1-23 1-24 1-25 1-26 1-4 Composition HFO-1132(E) 49.2 51.0 53.5 55.0 57.0 59.0 60.0 70.0 ratio HFO-1234yf 50.8 49.046.5 45.0 43.0 41.0 40.0 30.0 HFC-134a 0 0 0 0 0 0 0 0 HFC-143a 0 0 0 00 0 0 0 HFC-125 0 0 0 0 0 0 0 0 GWP (AR4) 7 7 7 7 7 8 8 8 Dischargetemperature 104.7 105.5 106.6 107.3 108.1 109.0 109.5 113.9 Saturationpressure 1.874 1.898 1.931 1.950 1.975 2.000 2.012 2.128 (40° C.)Evaporation pressure 0.164 0.167 0.171 0.174 0.177 0.180 0.181 0.196Compression ratio 11.4 11.4 11.3 11.2 11.2 11.1 11.1 10.8 COP ratio(relative to 104.5 104.4 104.4 104.4 104.3 104.3 104.3 104.3 R404A)Refrigerating capacity 108.0 109.8 112.3 113.8 115.7 117.7 118.6 128.0ratio (relative to R404A) ASHRAE flammability Class 2L Class 2L Class 2LClass 2 Class 2 Class 2 Class 2 Class 2 classification

Test Example 1-3

The GWP of each mixed refrigerant shown in Examples 1-27 to 1-39,Comparative Examples 1-5 to 1-6, and Reference Example 1-3 (R404A) wasevaluated based on the values in the IPCC fourth report.

The COP, refrigerating capacity, discharge temperature, saturationpressure at a saturation temperature of 40° C., condensation pressure,and evaporation pressure of each of the mixed refrigerants weredetermined by performing refrigeration cycle theoretical calculationsfor the mixed refrigerants by using NIST and Refprop 10.0 under thefollowing conditions.

Evaporation temperature: −10° C.

Condensation temperature: 40° C.

Superheating temperature: 20 K

Supercooling temperature: 0 K

Compressor efficiency: 70%

The definitions of the terms are the same as those in Test Example 1-1.

Table 3 shows the results of Test Example 1-3. Table 3 shows Examplesand Comparative Examples with regard to a Refrigerant 1 of the presentdisclosure. In Table 3, the definitions of the terms are the same asthose in Test Example 1-1.

The coefficient of performance (COP) and the compression ratio weredetermined as in Test Example 1-1.

The flammability of the mixed refrigerant was evaluated as in TestExample 1-1. The burning rate test was performed as in Test Example 1-1.

The flammable range of the mixed refrigerant was measured in the samemanner and under the same conditions as in Test Example 1-1 by using ameasurement device according to ASTM E681-09 (see FIG. 1 ).

TABLE 3 Reference Comparative Example 1-3 Example Example ExampleExample Example Example Example Item Unit (R404A) 1-5 1-27 1-28 1-291-30 1-31 1-32 Composition HFO-1132 (E) mass % 0 30.0 40.0 40.5 41.343.0 45.0 47.0 ratio HFO-1234yf mass % 0 70.0 60.0 59.5 58.7 57.0 55.053.0 HFC-134a mass % 4.0 0 0 0 0 0 0 0 HFC-143a mass % 52.0 0 0 0 0 0 00 HFC-125 mass % 44.0 0 0 0 0 0 0 0 GWP (AR4) — 3922 6 6 6 6 7 7 7Discharge temperature ° C. 75.8 80.8 83.7 83.9 84.1 84.5 85.1 85.6Saturation pressure MPa 1.822 1.592 1.745 1.752 1.764 1.788 1.817 1.844(40° C.) Evaporation pressure MPa 0.434 0.357 0.399 0.401 0.404 0.4110.419 0.427 Compression ratio — 4.2 4.5 4.4 4.4 4.4 4.3 4.3 4.3 COPratio (relative to % 100 103.8 102.9 102.9 102.8 102.7 102.5 102.4R404A) Refrigerating capacity % 100 89.8 98.7 99.1 99.8 101.2 102.8104.5 ratio (relative to R404A) ASHRAE flammability — Class 1 Class 2LClass 2L Class 2L Class 2L Class 2L Class 2L Class 2L classificationComparative Example Example Example Example Example Example ExampleExample Item 1-33 1-34 1-35 1-36 1-37 1-38 1-39 1-6 Composition HFO-1132(E) 49.2 51.0 53.5 55.0 57.0 59.0 60.0 70.0 ratio HFO-1234yf 50.8 49.046.5 45.0 43.0 41.0 40.0 30.0 HFC-134a 0 0 0 0 0 0 0 0 HFC-143a 0 0 0 00 0 0 0 HFC-125 0 0 0 0 0 0 0 0 GWP (AR4) 7 7 7 7 7 8 8 8 Dischargetemperature 86.2 86.6 87.3 87.7 88.2 88.7 88.9 91.5 Saturation pressure1.874 1.898 1.931 1.950 1.975 2.000 2.012 2.128 (40° C.) Evaporationpressure 0.436 0.443 0.452 0.457 0.465 0.472 0.475 0.509 Compressionratio 4.3 4.3 4.3 4.3 4.3 4.2 4.2 4.2 COP ratio (relative to 102.2 102.1102.0 101.9 101.8 101.7 101.6 101.3 R404A) Refrigerating capacity 106.2107.7 109.6 110.8 112.3 113.8 114.5 121.7 ratio (relative to R404A)ASHRAE flammability Class 2L Class 2L Class 2L Class 2 Class 2 Class 2Class 2 Class 2 classification

Test Example 1-4

The GWP of each mixed refrigerant shown in Comparative Examples 1-7 to1-21 and Reference Example 1-4 (R404A) was evaluated based on the valuesin the IPCC fourth report.

The COP, refrigerating capacity, discharge temperature, saturationpressure at a saturation temperature of 40° C., condensation pressure,and evaporation pressure of each of the mixed refrigerants weredetermined by performing refrigeration cycle theoretical calculationsfor the mixed refrigerants using NIST and Refprop 10.0 under thefollowing conditions.

Evaporation temperature: −80° C.

Condensation temperature: 40° C.

Superheating temperature: 20 K

Supercooling temperature: 0 K

Compressor efficiency: 70%

The definitions of the terms are the same as those in Test Example 1-1.

Table 4 shows the results of Test Example 1-4. Table 4 shows ComparativeExamples with regard to the Refrigerant 1 of the present disclosure. InTable 4, the definitions of the terms are the same as those in TestExample 1-1.

The coefficient of performance (COP) and the compression ratio weredetermined as in Test Example 1-1.

The flammability of the mixed refrigerant was evaluated as in TestExample 1-1. The burning rate test was performed as in Test Example 1-1.

The flammable range of the mixed refrigerant was measured in the samemanner and under the same conditions as in Test Example 1-1 by using ameasurement device according to ASTM E681-09 (see FIG. 1 ).

TABLE 4 Reference Example 1-4 Comp. Comp. Comp. Comp. Comp. Comp. Comp.Item Unit (R404A) Ex. 1-7 Ex. 1-8 Ex. 1-9 Ex. 1-10 Ex. 1-11 Ex. 1-12 Ex.1-13 Composition HFO-1132 (E) mass % 0 30.0 40.0 40.5 41.3 43.0 45.047.0 ratio HFO-1234yf mass % 0 70.0 60.0 59.5 58.7 57.0 55.0 53.0HFC-134a mass % 4.0 0 0 0 0 0 0 0 HFC-143a mass % 52.0 0 0 0 0 0 0 0HFC-125 mass % 44.0 0 0 0 0 0 0 0 GWP (AR4) — 3922 6 6 6 6 7 7 7Discharge temperature ° C. 136.7 146.0 157.7 158.1 158.8 160.4 162.1163.9 Saturation pressure MPa 1.822 1.592 1.745 1.752 1.764 1.788 1.8171.844 (40° C.) Evaporation pressure MPa 0.014 0.011 0.012 0.012 0.0120.012 0.013 0.013 Compression ratio — 134.6 149.1 150.8 150.2 149.3147.2 145.0 142.8 COP ratio (relative to % 100 112.6 110.3 110.3 110.4110.6 110.8 111.0 R404A) Refrigerating capacity % 100 91.7 99.3 100.2101.5 104.4 107.8 111.3 ratio (relative to R404A) ASHRAE flammability —Class 1 Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2Lclassification Comp. Comp. Comp. Comp. Comp. Comp. Comp. Comp. Item Ex.1-14 Ex. 1-15 Ex. 1-16 Ex. 1-17 Ex. 1-18 Ex. 1-19 Ex. 1-20 Ex. 1-21Composition HFO-1132 (E) 49.2 51.0 53.5 55.0 57.0 59.0 60.0 70.0 ratioHFO-1234yf 50.8 49.0 46.5 45.0 43.0 41.0 40.0 30.0 HFC-134a 0 0 0 0 0 00 0 HFC-143a 0 0 0 0 0 0 0 0 HFC-125 0 0 0 0 0 0 0 0 GWP (AR4) 7 7 7 7 78 8 8 Discharge temperature 165.8 167.4 169.6 170.9 172.6 174.3 175.2184.0 Saturation pressure 1.874 1.898 1.931 1.950 1.975 2.000 2.0122.128 (40° C.) Evaporation pressure 0.013 0.014 0.014 0.014 0.015 0.0150.015 0.017 Compression ratio 140.5 138.7 136.3 134.9 133.2 131.5 130.7123.8 COP ratio (relative to 111.3 111.4 111.7 111.9 112.1 112.3 112.4113.5 R404A) Refrigerating capacity 115.1 118.2 122.5 125.2 128.6 132.1133.8 151.0 ratio (relative to R404A) ASHRAE flammability Class 2L Class2L Class 2L Class 2 Class 2 Class 2 Class 2 Class 2 classification

Test Example 1-5

The GWP of each mixed refrigerant shown in Comparative Examples 1-22 to1-36 and Reference Example 1-5 (R404A) was evaluated based on the valuesin the IPCC fourth report.

The COP, refrigerating capacity, discharge temperature, saturationpressure at a saturation temperature of 40° C., condensation pressure,and evaporation pressure of each of the mixed refrigerants weredetermined by performing refrigeration cycle theoretical calculationsfor the mixed refrigerants using NIST and Refprop 10.0 under thefollowing conditions.

Evaporation temperature: 10° C.

Condensation temperature: 40° C.

Superheating temperature: 20 K

Supercooling temperature: 0 K

Compressor efficiency: 70%

The definitions of the terms are the same as those in Test Example 1-1.

Table 5 shows the results of Test Example 1-5. Table 5 shows ComparativeExamples with regard to the Refrigerant 1 of the present disclosure. InTable 5, the definitions of the terms are the same as those in TestExample 1-1.

The coefficient of performance (COP) and the compression ratio weredetermined as in Test Example 1-1.

The flammability of the mixed refrigerant was evaluated as in TestExample 1-1. The burning rate test was performed as in Test Example 1-1.

The flammable range of the mixed refrigerant was measured in the samemanner and under the same conditions as in Test Example 1-1 by using ameasurement device according to ASTM E681-09 (see FIG. 1 ).

TABLE 5 Reference Example 1-5 Comp. Comp. Comp. Comp. Comp. Comp. Comp.Item Unit (R404A) Ex. 1-22 Ex. 1-23 Ex. 1-24 Ex. 1-25 Ex. 1-26 Ex. 1-27Ex. 1-28 Composition HFO-1132 (E) mass % 0 30.0 40.0 40.5 41.3 43.0 45.047.0 ratio HFO-1234yf mass % 0 70.0 60.0 59.5 58.7 57.0 55.0 53.0HFC-134a mass % 4.0 0 0 0 0 0 0 0 HFC-143a mass % 52.0 0 0 0 0 0 0 0HFC-125 mass % 44.0 0 0 0 0 0 0 0 GWP (AR4) — 3922 6 6 6 6 7 7 7Discharge temperature ° C. 68.5 72.4 74.0 74.1 74.2 74.4 74.7 74.9Saturation pressure MPa 1.822 1.592 1.745 1.752 1.764 1.788 1.817 1.844(40° C.) Evaporation pressure MPa 0.820 0.694 0.768 0.772 0.777 0.7890.803 0.817 Compression ratio — 2.2 2.3 2.3 2.3 2.3 2.3 2.3 2.3 COPratio (relative to % 100.0 103.1 101.9 101.8 101.7 101.5 101.3 101.1R404A) Refrigerating capacity % 100.0 91.2 98.9 99.3 99.8 101.0 102.5103.8 ratio (relative to R404A) ASHRAE flammability — Class 1 Class 2LClass 2L Class 2L Class 2L Class 2L Class 2L Class 2L classificationComp. Comp. Comp. Comp. Comp. Comp. Comp. Comp. Item Ex. 1-29 Ex. 1-30Ex. 1-31 Ex. 1-32 Ex. 1-33 Ex. 1-34 Ex. 1-35 Ex. 1-36 CompositionHFO-1132 (E) 49.2 51.0 53.5 55.0 57.0 59.0 60.0 70.0 ratio HFO-1234yf50.8 49.0 46.5 45.0 43.0 41.0 40.0 30.0 HFC-134a 0 0 0 0 0 0 0 0HFC-143a 0 0 0 0 0 0 0 0 HFC-125 0 0 0 0 0 0 0 0 GWP (AR4) 7 7 7 7 7 8 88 Discharge temperature 75.2 75.5 75.8 76.0 76.2 76.5 76.6 77.9Saturation pressure 1.874 1.898 1.931 1.950 1.975 2.000 2.012 2.128 (40°C.) Evaporation pressure 0.832 0.844 0.860 0.870 0.882 0.895 0.901 0.959Compression ratio 2.3 2.2 2.2 2.2 2.2 2.2 2.2 2.2 COP ratio (relative to100.9 100.8 100.6 100.4 100.3 100.1 100.1 99.5 R404A) Refrigeratingcapacity 105.3 106.5 108.2 109.1 110.4 111.6 112.3 118.2 ratio (relativeto R404A) ASHRAE flammability Class 2L Class 2L Class 2L Class 2 Class 2Class 2 Class 2 Class 2 classification

Test Example 2-1

The GWP of each mixed refrigerant shown in Examples 2-1 to 2-6,Comparative Examples 2-1 to 2-9, and Reference Example 2-1 (R404A) wasevaluated based on the values in the IPCC fourth report.

The COP, refrigerating capacity, discharge temperature, saturationpressure at a saturation temperature of 40° C., condensation pressure,and evaporation pressure of each of the mixed refrigerants weredetermined by performing refrigeration cycle theoretical calculationsfor the mixed refrigerants by using the National Institute of Scienceand Technology (NIST) and Reference Fluid Thermodynamic and TransportProperties Database (Refprop 10.0) under the following conditions.

Evaporation temperature: −50° C.

Condensation temperature: 40° C.

Superheating temperature: 20 K

Supercooling temperature: 0 K

Compressor efficiency: 70%

The “evaporation temperature of −50° C.” means that the evaporationtemperature of the mixed refrigerant in the evaporator provided in therefrigeration apparatus is −50° C. Further, the “condensationtemperature of 40° C.” means that the condensation temperature of themixed refrigerant in the condenser provided in the refrigerationapparatus is 40° C.

Table 6 shows the results of Test Example 2-1. Table 6 shows Examplesand Comparative Examples with regard to a Refrigerant 2 of the presentdisclosure. In Table 6, the “COP ratio” and the “refrigerating capacityratio” refer to a ratio (%) relative to R404A. In Table 6, the“saturation pressure (40° C.)” refers to a saturation pressure at asaturation temperature of 40° C. In Table 6, the “discharge temperature(° C.)” refers to a temperature at which the refrigerant has the highesttemperature in the refrigeration cycle according to the refrigerationcycle theoretical calculations of the mixed refrigerant.

The coefficient of performance (COP) was calculated according to thefollowing equation.COP=(refrigerating capacity or heating capacity)/amount of electricalpower consumed

The compression ratio was calculated according to the followingequation.Compression ratio=condensation pressure(Mpa)/evaporation pressure(Mpa)

The flammability of the mixed refrigerant was determined by specifyingthe fractionation of the mixed refrigerant to the WCF concentration andmeasuring the burning rate according to ANSI/ASHRAE Standard 34-2013.The one with a burning rate of 0 cm/s to 10 cm/s was classified as Class2L (slightly flammable), the one with a burning rate of more than 10cm/s was classified as Class 2 (weakly flammable), and the one with noflame propagation was classified as Class 1 (non-flammable). In Table 6,the ASHRAE flammability classification shows the results based on thesecriteria.

The burning rate test was performed as follows. First, a mixedrefrigerant having a purity of 99.5% or more was used, and the mixedrefrigerant was deaerated by repeating a cycle of freezing, pumping, andthawing until no trace of air was observed on the vacuum gauge. Theburning rate was measured by a closed method. The initial temperaturewas the ambient temperature. The ignition was performed by generating anelectrical spark between the electrodes in the center of the samplecell. The duration of the discharge was 1.0 to 9.9 ms, and the ignitionenergy was typically about 0.1 to 1.0 J. The spread of the flame wasvisualized by using a schlieren photograph. A cylindrical container(inner diameter: 155 mm, length: 198 mm) having two acrylic windows thattransmit light was used as a sample cell, and a xenon lamp was used as alight source. The schlieren image of the flame was recorded using ahigh-speed digital video camera at a frame speed of 600 fps, and storedin a PC.

The flammable range of the mixed refrigerant was measured using ameasurement device according to ASTM E681-09 (see FIG. 1 ).

More specifically, a 12-L spherical glass flask was used so that thecombustion state could be visually observed and photographicallyrecorded. When excessive pressure was generated by combustion in theglass flask, gas was allowed to escape from the upper lid. Ignition wasachieved by electric discharge from electrodes disposed at one-third thedistance from the bottom.

Test Conditions

Test vessel: 280-mm ϕ spherical (internal volume: 12 liters)

Test temperature: 60° C.±3° C.

Pressure: 101.3 kPa±0.7 kPa

Water: 0.0088 g±0.0005 g (water content at a relative humidity of 50% at23° C.) per gram of dry air

Mixing ratio of refrigerant composition/air: 1 vol. % increments±0.2vol. %

Mixture of refrigerant composition: ±0.1 mass %

Ignition method: AC discharge, voltage: 15 kV, electric current: 30 mA,neon transformer

Electrode spacing: 6.4 mm (¼ inch)

Spark: 0.4 seconds±0.05 seconds

Evaluation Criteria:

When the flame spread at an angle of more than 90° from the ignitionpoint, it was evaluated that flame propagation was present (flammable).

When the flame spread at an angle of 90° or less from the ignitionpoint, it was evaluated that flame propagation was absent(non-flammable).

TABLE 6 Reference Example 2-1 Comp. Comp. Example Example ExampleExample Example Item Unit (R404A) Ex. 2-1 Ex. 2-2 2-1 2-2 2-3 2-4 2-5Composition HFO-1132 (E) mass % 0 30.0 40.0 40.5 41.3 43.0 45.0 47.0ratio HFO-1234yf mass % 0 70.0 60.0 59.5 58.7 57.0 55.0 53.0 HFC-134amass % 4.0 0 0 0 0 0 0 0 HFC-143a mass % 52.0 0 0 0 0 0 0 0 HFC-125 mass% 44.0 0 0 0 0 0 0 0 GWP (AR4) — 3922 6 6 6 6 7 7 7 Dischargetemperature ° C. 100.6 108.6 114.7 115.0 115.5 116.5 117.6 118.8Saturation pressure MPa 1.822 1.592 1.745 1.752 1.764 1.788 1.817 1.844(40° C.) Evaporation pressure MPa 0.082 0.063 0.072 0.073 0.074 0.0750.077 0.079 Compression ratio — 22.2 25.3 24.1 24.0 23.9 23.8 23.6 23.4COP ratio (relative to % 100 106.2 106.2 106.2 106.2 106.2 106.2 106.2R404A) Refrigerating capacity % 100 86.2 98.5 99.1 100 102.1 104.5 106.9ratio (relative to R404A) ASHRAE flammability — Class 1 Class 2L Class2L Class 2L Class 2L Class 2L Class 2L Class 2L classification ExampleComp. Comp. Comp. Comp. Comp. Comp. Comp. Item 2-6 Ex. 2-3 Ex. 2-4 Ex.2-5 Ex. 2-6 Ex. 2-7 Ex. 2-8 Ex. 2-9 Composition HFO-1132 (E) 49.2 51.053.5 55.0 57.0 59.0 60.0 70.0 ratio HFO-1234yf 50.8 49.0 46.5 45.0 43.041.0 40.0 30.0 HFC-134a 0 0 0 0 0 0 0 0 HFC-143a 0 0 0 0 0 0 0 0 HFC-1250 0 0 0 0 0 0 0 GWP (AR4) 7 7 7 7 7 8 8 8 Discharge temperature 120.0121.0 122.4 123.3 124.4 125.5 126.0 131.7 Saturation pressure 1.8741.898 1.931 1.950 1.975 2.000 2.012 2.128 (40° C.) Evaporation pressure0.081 0.083 0.085 0.086 0.088 0.090 0.091 0.099 Compression ratio 23.123.0 22.8 22.6 22.5 22.3 22.2 21.6 COP ratio (relative to 106.2 106.3106.3 106.3 106.3 106.4 106.4 106.7 R404A) Refrigerating capacity 109.5111.7 114.6 116.4 118.7 121 122.2 133.3 ratio (relative to R404A) ASHRAEflammability Class 2L Class 2L Class 2L Class 2 Class 2 Class 2 Class 2Class 2 classification

Test Example 2-2

The GWP of each mixed refrigerant shown in Examples 2-7 to 2-12,Comparative Examples 2-10 to 1-18, and Reference Example 2-2 (R404A) wasevaluated based on the values in the IPCC fourth report.

The COP, refrigerating capacity, discharge temperature, saturationpressure at a saturation temperature of 40° C., condensation pressure,and evaporation pressure of each of the mixed refrigerants weredetermined by performing refrigeration cycle theoretical calculationsfor the mixed refrigerants by using NIST and Refprop 10.0 under thefollowing conditions.

Evaporation temperature: −35° C.

Condensation temperature: 40° C.

Superheating temperature: 20 K

Supercooling temperature: 0 K

Compressor efficiency: 70%

The definitions of the terms are the same as those in Test Example 2-1.

Table 7 shows the results of Test Example 2-2. Table 7 shows Examplesand Comparative Examples with regard to a Refrigerant 2 of the presentdisclosure. In Table 7, the definitions of the terms are the same asthose in Test Example 2-1.

The coefficient of performance (COP) and the compression ratio weredetermined as in Test Example 2-1.

The flammability of the mixed refrigerant was evaluated as in TestExample 2-1. The burning rate test was performed as in Test Example 2-1.

The flammable range of the mixed refrigerant was measured in the samemanner and under the same conditions as in Test Example 2-1 using ameasurement device according to ASTM E681-09 (see FIG. 1 ).

TABLE 7 Reference Example 2-2 Comp. Comp. Example Example ExampleExample Example Item Unit (R404A) Ex. 2-10 Ex. 2-11 2-7 2-8 2-9 2-102-11 Composition HFO-1132 (E) mass % 0 30.0 40.0 40.5 41.3 43.0 45.047.0 ratio HFO-1234yf mass % 0 70.0 60.0 59.5 58.7 57.0 55.0 53.0HFC-134a mass % 4.0 0 0 0 0 0 0 0 HFC-143a mass % 52.0 0 0 0 0 0 0 0HFC-125 mass % 44.0 0 0 0 0 0 0 0 GWP (AR4) — 3922 6 6 6 6 7 7 7Discharge temperature ° C. 89.1 95.8 100.6 100.8 101.2 102.0 102.9 103.8Saturation pressure MPa 1.822 1.592 1.745 1.752 1.764 1.788 1.817 1.844(40° C.) Evaporation pressure MPa 0.165 0.131 0.148 0.149 0.151 0.1540.157 0.160 Compression ratio — 11.0 12.2 11.8 11.7 11.7 11.6 11.6 11.5COP ratio (relative to % 100 105.1 104.8 104.7 104.7 104.7 104.6 104.5R404A) Refrigerating capacity % 100 87.7 98.5 99.0 99.8 101.6 103.7105.7 ratio (relative to R404A) ASHRAE flammability — Class 1 Class 2LClass 2L Class 2L Class 2L Class 2L Class 2L Class 2L classificationExample Comp. Comp. Comp. Comp. Comp. Comp. Comp. Item 2-12 Ex. 2-12 Ex.2-13 Ex. 2-14 Ex. 2-15 Ex. 2-16 Ex. 2-17 Ex. 2-18 Composition HFO-1132(E) 49.2 51.0 53.5 55.0 57.0 59.0 60.0 70.0 ratio HFO-1234yf 50.8 49.046.5 45.0 43.0 41.0 40.0 30.0 HFC-134a 0 0 0 0 0 0 0 0 HFC-143a 0 0 0 00 0 0 0 HFC-125 0 0 0 0 0 0 0 0 GWP (AR4) 7 7 7 7 7 8 8 8 Dischargetemperature 104.7 105.5 106.6 107.3 108.1 109.0 109.5 113.9 Saturationpressure 1.874 1.898 1.931 1.950 1.975 2.000 2.012 2.128 (40° C.)Evaporation pressure 0.164 0.167 0.171 0.174 0.177 0.180 0.181 0.196Compression ratio 11.4 11.4 11.3 11.2 11.2 11.1 11.1 10.8 COP ratio(relative to 104.5 104.4 104.4 104.4 104.3 104.3 104.3 104.3 R404A)Refrigerating capacity 108.0 109.8 112.3 113.8 115.7 117.7 118.6 128.0ratio (relative to R404A) ASHRAE flammability Class 2L Class 2L Class 2LClass 2 Class 2 Class 2 Class 2 Class 2 classification

Test Example 2-3

The GWP of each mixed refrigerant shown in Examples 2-13 to 2-18,Comparative Examples 2-19 to 2-27, and Reference Example 2-3 (R404A) wasevaluated based on the values in the IPCC fourth report.

The COP, refrigerating capacity, discharge temperature, saturationpressure at a saturation temperature of 40° C., condensation pressure,and evaporation pressure of each of the mixed refrigerants weredetermined by performing refrigeration cycle theoretical calculationsfor the mixed refrigerants using NIST and Refprop 10.0 under thefollowing conditions.

Evaporation temperature: −10° C.

Condensation temperature: 40° C.

Superheating temperature: 20 K

Supercooling temperature: 0 K

Compressor efficiency: 70%

The definitions of the terms are the same as those in Test Example 2-1.

Table 8 shows the results of Test Example 2-3. Table 8 shows Examplesand Comparative Examples with regard to a Refrigerant 2 of the presentdisclosure. In Table 8, the definitions of the terms are the same asthose in Test Example 2-1.

The coefficient of performance (COP) and the compression ratio weredetermined as in Test Example 2-1.

The flammability of the mixed refrigerant was evaluated as in TestExample 2-1. The burning rate test was performed as in Test Example 2-1.

The flammable range of the mixed refrigerant was measured in the samemanner and under the same conditions as in Test Example 2-1 by using ameasurement device according to ASTM E681-09 (see FIG. 1 ).

TABLE 8 Reference Example 2-3 Comp. Comp. Example Example ExampleExample Example Item Unit (R404A) Ex. 2-19 Ex. 2-20 2-13 2-14 2-15 2-162-17 Composition HFO-1132 (E) mass % 0 30.0 40.0 40.5 41.3 43.0 45.047.0 ratio HFO-1234yf mass % 0 70.0 60.0 59.5 58.7 57.0 55.0 53.0HFC-134a mass % 4.0 0 0 0 0 0 0 0 HFC-143a mass % 52.0 0 0 0 0 0 0 0HFC-125 mass % 44.0 0 0 0 0 0 0 0 GWP (AR4) — 3922 6 6 6 6 7 7 7Discharge temperature ° C. 75.8 80.8 83.7 83.9 84.1 84.5 85.1 85.6Saturation pressure MPa 1.822 1.592 1.745 1.752 1.764 1.788 1.817 1.844(40° C.) Evaporation pressure MPa 0.434 0.357 0.399 0.401 0.404 0.4110.419 0.427 Compression ratio — 4.2 4.5 4.4 4.4 4.4 4.3 4.3 4.3 COPratio (relative to % 100 103.8 102.9 102.9 102.8 102.7 102.5 102.4R404A) Refrigerating capacity % 100 89.8 98.7 99.1 99.8 101.2 102.8104.5 ratio (relative to R404A) ASHRAE flammability — Class 1 Class 2LClass 2L Class 2L Class 2L Class 2L Class 2L Class 2L classificationExample Comp. Comp. Comp. Comp. Comp. Comp. Comp. Item 2-18 Ex. 2-21 Ex.2-22 Ex. 2-23 Ex. 2-24 Ex. 2-25 Ex. 2-26 Ex. 2-27 Composition HFO-1132(E) 49.2 51.0 53.5 55.0 57.0 59.0 60.0 70.0 ratio HFO-1234yf 50.8 49.046.5 45.0 43.0 41.0 40.0 30.0 HFC-134a 0 0 0 0 0 0 0 0 HFC-143a 0 0 0 00 0 0 0 HFC-125 0 0 0 0 0 0 0 0 GWP (AR4) 7 7 7 7 7 8 8 8 Dischargetemperature 86.2 86.6 87.3 87.7 88.2 88.7 88.9 91.5 Saturation pressure1.874 1.898 1.931 1.950 1.975 2.000 2.012 2.128 (40° C.) Evaporationpressure 0.436 0.443 0.452 0.457 0.465 0.472 0.475 0.509 Compressionratio 4.3 4.3 4.3 4.3 4.3 4.2 4.2 4.2 COP ratio (relative to 102.2 102.1102.0 101.9 101.8 101.7 101.6 101.3 R404A) Refrigerating capacity 106.2107.7 109.6 110.8 112.3 113.8 114.5 121.7 ratio (relative to R404A)ASHRAE flammability Class 2L Class 2L Class 2L Class 2 Class 2 Class 2Class 2 Class 2 classification

Test Example 2-4

The GWP of each mixed refrigerant shown in Examples 2-19 to 2-24,Comparative Examples 2-28 to 2-36, and Reference Example 2-4 (R404A) wasevaluated based on the values in the IPCC fourth report.

The COP, refrigerating capacity, discharge temperature, saturationpressure at a saturation temperature of 40° C., condensation pressure,and evaporation pressure of each of the mixed refrigerants weredetermined by performing refrigeration cycle theoretical calculationsfor the mixed refrigerants using NIST and Refprop 10.0 under thefollowing conditions.

Evaporation temperature: −80° C.

Condensation temperature: 40° C.

Superheating temperature: 20 K

Supercooling temperature: 0 K

Compressor efficiency: 70%

The definitions of the terms are the same as those in Test Example 2-1.

Table 9 shows the results of Test Example 2-4. Table 9 shows Examplesand Comparative Examples with regard to a Refrigerant 2 of the presentdisclosure. In Table 9, the definitions of the terms are the same asthose in Test Example 2-1.

The coefficient of performance (COP) and the compression ratio weredetermined as in Test Example 2-1.

The flammability of the mixed refrigerant was evaluated as in TestExample 2-1. The burning rate test was performed as in Test Example 2-1.

The flammable range of the mixed refrigerant was measured in the samemanner and under the same conditions as in Test Example 2-1 by using ameasurement device according to ASTM E681-09 (see FIG. 1 ).

TABLE 9 Reference Example 2-4 Comp. Comp. Example Example ExampleExample Example Item Unit (R404A) Ex. 2-28 Ex. 2-29 2-19 2-20 2-21 2-222-23 Composition HFO-1132 (E) mass % 0 30.0 40.0 40.5 41.3 43.0 45.047.0 ratio HFO-1234yf mass % 0 70.0 60.0 59.5 58.7 57.0 55.0 53.0HFC-134a mass % 4.0 0 0 0 0 0 0 0 HFC-143a mass % 52.0 0 0 0 0 0 0 0HFC-125 mass % 44.0 0 0 0 0 0 0 0 GWP (AR4) — 3922 6 6 6 6 7 7 7Discharge temperature ° C. 136.7 146.0 157.7 158.1 158.8 160.4 162.1163.9 Saturation pressure MPa 1.822 1.592 1.745 1.752 1.764 1.788 1.8171.844 (40° C.) Evaporation pressure MPa 0.014 0.011 0.012 0.012 0.0120.012 0.013 0.013 Compression ratio — 134.6 149.1 150.8 150.2 149.3147.2 145.0 142.8 COP ratio (relative to % 100 112.6 110.3 110.3 110.4110.6 110.8 111.0 R404A) Refrigerating capacity % 100 91.7 99.3 100.2101.5 104.4 107.8 111.3 ratio (relative to R404A) ASHRAE flammability —Class 1 Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2Lclassification Example Comp. Comp. Comp. Comp. Comp. Comp. Comp. Item2-24 Ex. 2-30 Ex. 2-31 Ex. 2-32 Ex. 2-33 Ex. 2-34 Ex. 2-35 Ex. 2-36Composition HFO-1132 (E) 49.2 51.0 53.5 55.0 57.0 59.0 60.0 70.0 ratioHFO-1234yf 50.8 49.0 46.5 45.0 43.0 41.0 40.0 30.0 HFC-134a 0 0 0 0 0 00 0 HFC-143a 0 0 0 0 0 0 0 0 HFC-125 0 0 0 0 0 0 0 0 GWP (AR4) 7 7 7 7 78 8 8 Discharge temperature 165.8 167.4 169.6 170.9 172.6 174.3 175.2184.0 Saturation pressure 1.874 1.898 1.931 1.950 1.975 2.000 2.0122.128 (40° C.) Evaporation pressure 0.013 0.014 0.014 0.014 0.015 0.0150.015 0.017 Compression ratio 140.5 138.7 136.3 134.9 133.2 131.5 130.7123.8 COP ratio (relative to 111.3 111.4 111.7 111.9 112.1 112.3 112.4113.5 R404A) Refrigerating capacity 115.1 118.2 122.5 125.2 128.6 132.1133.8 151.0 ratio (relative to R404A) ASHRAE flammability Class 2L Class2L Class 2L Class 2 Class 2 Class 2 Class 2 Class 2 classification

Test Example 2-5

The GWP of each mixed refrigerant shown in Examples 2-25 to 2-30,Comparative Examples 2-37 to 2-45, and Reference Example 2-5 (R404A) wasevaluated based on the values in the IPCC fourth report.

The COP, refrigerating capacity, discharge temperature, saturationpressure at a saturation temperature of 40° C., condensation pressure,and evaporation pressure of each of the mixed refrigerants weredetermined by performing refrigeration cycle theoretical calculationsfor the mixed refrigerants by using NIST and Refprop 10.0 under thefollowing conditions.

Evaporation temperature: 10° C.

Condensation temperature: 40° C.

Superheating temperature: 20 K

Supercooling temperature: 0 K

Compressor efficiency: 70%

The definitions of the terms are the same as those in Test Example 2-1.

Table 10 shows the results of Test Example 2-5. Table 10 shows Examplesand Comparative Examples with regard to a Refrigerant 2 of the presentdisclosure. In Table 10, the definitions of the terms are the same asthose in Test Example 2-1.

The coefficient of performance (COP) and the compression ratio weredetermined as in Test Example 2-1.

The flammability of the mixed refrigerant was evaluated as in TestExample 2-1. The burning rate test was performed as in Test Example 2-1.

The flammable range of the mixed refrigerant was measured in the samemanner and under the same conditions as in Test Example 2-1 by using ameasurement device according to ASTM E681-09 (see FIG. 1 ).

TABLE 10 Reference Example 2-5 Comp. Comp. Example Example ExampleExample Example Item Unit (R404A) Ex. 2-37 Ex. 2-38 2-25 2-26 2-27 2-282-29 Composition HFO-1132 (E) mass % 0 30.0 40.0 40.5 41.3 43.0 45.047.0 ratio HFO-1234yf mass % 0 70.0 60.0 59.5 58.7 57.0 55.0 53.0HFC-134a mass % 4.0 0 0 0 0 0 0 0 HFC-143a mass % 52.0 0 0 0 0 0 0 0HFC-125 mass % 44.0 0 0 0 0 0 0 0 GWP (AR4) — 3922 6 6 6 6 7 7 7Discharge temperature ° C. 68.5 72.4 74.0 74.1 74.2 74.4 74.7 74.9Saturation pressure MPa 1.822 1.592 1.745 1.752 1.764 1.788 1.817 1.844(40° C.) Evaporation pressure MPa 0.820 0.694 0.768 0.772 0.777 0.7890.803 0.817 Compression ratio — 2.2 2.3 2.3 2.3 2.3 2.3 2.3 2.3 COPratio (relative to % 100.0 103.1 101.9 101.8 101.7 101.5 101.3 101.1R404A) Refrigerating capacity % 100.0 91.2 98.9 99.3 99.8 101.0 102.5103.8 ratio (relative to R404A) ASHRAE flammability — Class 1 Class 2LClass 2L Class 2L Class 2L Class 2L Class 2L Class 2L classificationExample Comp. Comp. Comp. Comp. Comp. Comp. Comp. Item 2-30 Ex. 2-39 Ex.2-40 Ex. 2-41 Ex. 2-42 Ex. 2-43 Ex. 2-44 Ex. 2-45 Composition HFO-1132(E) 49.2 51.0 53.5 55.0 57.0 59.0 60.0 70.0 ratio HFO-1234yf 50.8 49.046.5 45.0 43.0 41.0 40.0 30.0 HFC-134a 0 0 0 0 0 0 0 0 HFC-143a 0 0 0 00 0 0 0 HFC-125 0 0 0 0 0 0 0 0 GWP (AR4) 7 7 7 7 7 8 8 8 Dischargetemperature 75.2 75.5 75.8 76.0 76.2 76.5 76.6 77.9 Saturation pressure1.874 1.898 1.931 1.950 1.975 2.000 2.012 2.128 (40° C.) Evaporationpressure 0.832 0.844 0.860 0.870 0.882 0.895 0.901 0.959 Compressionratio 2.3 2.2 2.2 2.2 2.2 2.2 2.2 2.2 COP ratio (relative to 100.9 100.8100.6 100.4 100.3 100.1 100.1 99.5 R404A) Refrigerating capacity 105.3106.5 108.2 109.1 110.4 111.6 112.3 118.2 ratio (relative to R404A)ASHRAE flammability Class 2L Class 2L Class 2L Class 2 Class 2 Class 2Class 2 Class 2 classification

Test Example 3

The GWP of each mixed refrigerant shown in Examples 3-1 to 3-5,Comparative Examples 3-1 to 3-5, and Reference Examples 3-1(R134a) and3-2 (R404A) was evaluated based on the values in the IPCC fourth report.

The COP, refrigerating capacity, discharge temperature, saturationpressure at a saturation temperature of 45° C., condensation pressure,and evaporation pressure of each of the mixed refrigerants weredetermined by performing refrigeration cycle theoretical calculationsfor the mixed refrigerants by using the National Institute of Scienceand Technology (NIST) and Reference Fluid Thermodynamic and TransportProperties Database (Refprop 10.0) under the following conditions.

Evaporation temperature: −10° C.

Condensation temperature: 45° C.

Superheating temperature: 20 K

Supercooling temperature: 0 K

Compressor efficiency: 70%

The “evaporation temperature of −10° C.” means that the evaporationtemperature of the mixed refrigerant in the evaporator provided in therefrigeration apparatus is −10° C. Further, the “condensationtemperature of 45° C.” means that the condensation temperature of themixed refrigerant in the condenser provided in the refrigerationapparatus is 45° C.

Table 11 shows the results of Test Example 3. Table 11 shows Examplesand Comparative Examples with regard to a refrigerant 3 of the presentdisclosure. In Table 11, the “COP ratio” and the “refrigerating capacityratio” refer to a ratio (%) relative to R134a. In Table 11, the“saturation pressure (45° C.)” refers to a saturation pressure at asaturation temperature of 45° C. In Table 11, the “discharge temperature(° C.)” refers to a temperature at which the refrigerant has the highesttemperature in the refrigeration cycle according to the refrigerationcycle theoretical calculations of the mixed refrigerant.

The coefficient of performance (COP) was calculated according to thefollowing equation.COP=(refrigerating capacity or heating capacity)/amount of electricalpower consumed

The critical temperature was determined by performing calculations usingthe National Institute of Science and Technology (NIST) and ReferenceFluid Thermodynamic and Transport Properties Database (Refprop 10.0).

The flammability of the mixed refrigerant was determined by specifyingthe fractionation of the mixed refrigerant to the WCF concentration andmeasuring the burning rate according to ANSI/ASHRAE Standard 34-2013.The one with a burning rate of 0 cm/s to 10 cm/s was classified as Class2L (slightly flammable), the one with a burning rate of more than 10cm/s was classified as Class 2 (weakly flammable), and the one with noflame propagation was classified as Class 1 (non-flammable). In Table11, the ASHRAE flammability classification shows the results based onthese criteria.

The burning rate test was performed as follows. First, a mixedrefrigerant having a purity of 99.5% or more was used, and the mixedrefrigerant was deaerated by repeating a cycle of freezing, pumping, andthawing until no trace of air was observed on the vacuum gauge. Theburning rate was measured by a closed method. The initial temperaturewas the ambient temperature. The ignition was performed by generatingelectrical spark between the electrodes in the center of the samplecell. The duration of the discharge was 1.0 to 9.9 ms, and the ignitionenergy was typically about 0.1 to 1.0 J. The spread of the flame wasvisualized by using a schlieren photograph. A cylindrical container(inner diameter: 155 mm, length: 198 mm) having two acrylic windows thattransmit light was used as a sample cell, and a xenon lamp was used as alight source. The schlieren image of the flame was recorded using ahigh-speed digital video camera at a frame speed of 600 fps, and storedin a PC.

The flammable range of the mixed refrigerant was measured using ameasurement device according to ASTM E681-09 (see FIG. 1 ).

More specifically, a 12-L spherical glass flask was used so that thecombustion state could be visually observed and photographicallyrecorded. When excessive pressure was generated by combustion in theglass flask, gas was allowed to escape from the upper lid. Ignition wasachieved by electric discharge from electrodes disposed at one-third thedistance from the bottom.

Test Conditions

Test vessel: 280 mm ϕ spherical (internal volume: 12 liters)

Test temperature: 60° C.±3° C.

Pressure: 101.3 kPa±0.7 kPa

Water: 0.0088 g±0.0005 g (water content at a relative humidity of 50% at23° C.) per gram of dry air

Mixing ratio of refrigerant composition/air: 1 vol. % increments±0.2vol. %

Mixture of refrigerant composition: ±0.1 mass %

Ignition method: AC discharge, voltage: 15 kV, electric current: 30 mA,neon transformer

Electrode spacing: 6.4 mm (¼ inch)

Spark: 0.4 seconds±0.05 seconds

Evaluation Criteria:

When the flame spreads at an angle of more than 90° from the ignitionpoint, it was evaluated that flame propagation was present (flammable).

When the flame spreads at an angle of 90° or less from the ignitionpoint, it was evaluated that flame propagation was absent(non-flammable).

TABLE 11 Reference Example 3-1 Comp. Comp. Example Example Example ItemUnit (R134a) Ex. 3-1 Ex. 3-2 3-1 3-2 3-3 Composition HFO-1132 (E) mass %0 20.0 30.0 31.1 33.0 35.0 ratio HFO-1234yf mass % 0 80.0 70.0 68.9 67.065.0 HFC-134a mass % 100.0 0 0 0 0 0 HFC-143a mass % 0 0 0 0 0 0 HFC-125mass % 0 0 0 0 0 0 GWP (AR4) — 1430 5 6 6 6 6 Discharge temperature ° C.86.9 86.3 86.9 87.2 87.9 88.5 Saturation pressure MPa 1.160 1.607 1.7951.814 1.848 1.883 (45° C.) Evaporation pressure MPa 0.201 0.311 0.3550.360 0.368 0.376 Critical temperature ° C. 101.1 84.6 83.0 82.7 82.281.7 COP ratio (relative to % 100.0 93.6 92.7 92.6 92.4 92.2 R134a)Refrigerating capacity % 100.0 132.3 148.3 150.0 152.8 155.8 ratio(relative to R134a) ASHRAE flammability — Class 1 Class 2L Class 2LClass 2L Class 2L Class 2L classification Reference Example ExampleComp. Comp. Comp. Example 3-2 Item 3-4 3-5 Ex. 3-3 Ex. 3-4 Ex. 3-5(R404A) Composition HFO-1132 (E) 37.9 39.8 40.0 50.0 0.0 0 ratioHFO-1234yf 62.1 60.2 60.0 50.0 100.0 0 HFC-134a 0 0 0 0 0 4.0 HFC-143a 00 0 0 0 52.0 HFC-125 0 0 0 0 0 44.0 GWP (AR4) 6 6 6 7 4 3922 Dischargetemperature 89.4 90.0 90.1 93.0 72.2 81.7 Saturation pressure 1.9301.963 1.966 2.123 1.154 2.052 (45° C.) Evaporation pressure 0.388 0.3970.397 0.437 0.222 0.434 Critical temperature 81.0 80.5 80.5 78.7 94.772.0 COP ratio (relative to 92.0 91.8 91.8 91.0 95.7 88.6 R134a)Refrigerating capacity 159.8 162.7 162.9 176.6 96.2 164.4 ratio(relative to R134a) ASHRAE flammability Class 2L Class 2L Class 2L Class2L Class 2L Class 1 classification

Test Example 4

The GWP of each mixed refrigerant shown in Examples 4-1 to 4-7 andComparative Examples 4-1 to 4-5 was evaluated based on the values in theIPCC fourth report.

The COP, refrigerating capacity, discharge temperature, and saturationpressure at a saturation temperature of −10° C. of each of the mixedrefrigerants were determined by performing refrigeration cycletheoretical calculations for the mixed refrigerants using the NationalInstitute of Science and Technology (NIST) and Reference FluidThermodynamic and Transport Properties Database (Refprop 10.0) under thefollowing conditions.

Evaporation temperature: 5° C.

Condensation temperature: 45° C.

Superheating temperature: 5 K

Supercooling temperature: 5 K

Compressor efficiency: 70%

The “evaporation temperature of 5° C.” means that the evaporationtemperature of the mixed refrigerant in the evaporator provided in therefrigeration apparatus is 5° C. Further, the “condensation temperatureof 45° C.” means that the condensation temperature of the mixedrefrigerant in the condenser provided in the refrigeration apparatus is45° C.

Table 12 shows the results of Test Example 4. Table 12 shows Examplesand Comparative Examples with regard to a refrigerant 4 of the presentdisclosure. In Table 12, the “COP ratio” and the “refrigerating capacityratio” refer to a ratio (%) relative to R1234yf. In Table 12, the“saturation pressure (−10° C.)” refers to a saturation pressure at asaturation temperature of −10° C., which is a typical value of theevaporation temperature in the refrigeration condition. In Table 12, the“discharge temperature (° C.)” refers to a temperature at which therefrigerant has the highest temperature in the refrigeration cycletheoretical calculations of the mixed refrigerant.

The coefficient of performance (COP) was calculated according to thefollowing equation.COP=(refrigerating capacity or heating capacity)/amount of electricalpower consumed

The critical temperature was determined by performing calculations usingthe National Institute of Science and Technology (NIST) and ReferenceFluid Thermodynamic and Transport Properties Database (Refprop 10.0).

The flammability of the mixed refrigerant was determined by specifyingthe fractionation of the mixed refrigerant to the WCF concentration andmeasuring the burning rate according to ANSI/ASHRAE Standard 34-2013.The one with a burning rate of 0 cm/s to 10 cm/s was classified as Class2L (slightly flammable), the one with a burning rate of more than 10cm/s was classified as Class 2 (weakly flammable), and the one with noflame propagation was classified as Class 1 (non-flammable). In Table12, the ASHRAE flammability classification shows the results based onthese criteria.

The burning rate test was performed as follows. First, a mixedrefrigerant having a purity of 99.5% or more was used, and the mixedrefrigerant was deaerated by repeating a cycle of freezing, pumping, andthawing until no trace of air was observed on the vacuum gauge. Theburning rate was measured by a closed method. The initial temperaturewas the ambient temperature. The ignition was performed by generating anelectrical spark between the electrodes in the center of the samplecell. The duration of the discharge was 1.0 to 9.9 ms, and the ignitionenergy was typically about 0.1 to 1.0 J. The spread of the flame wasvisualized by using a schlieren photograph. A cylindrical container(inner diameter: 155 mm, length: 198 mm) having two acrylic windows thattransmit light was used as a sample cell, and a xenon lamp was used as alight source. The schlieren image of the flame was recorded using ahigh-speed digital video camera at a frame speed of 600 fps, and storedin a PC.

The flammable range of the mixed refrigerant was measured using ameasurement device according to ASTM E681-09 (see FIG. 1 ).

More specifically, a 12-L spherical glass flask was used so that thecombustion state could be visually observed and photographicallyrecorded. When excessive pressure was generated by combustion in theglass flask, gas was allowed to escape from the upper lid. Ignition wasachieved by electric discharge from electrodes disposed at one-third thedistance from the bottom.

Test Conditions

Test vessel: 280 mm ϕ spherical (internal volume: 12 liters)

Test temperature: 60° C.±3° C.

Pressure: 101.3 kPa±0.7 kPa

Water: 0.0088 g±0.0005 g (water content at a relative humidity of 50% at23° C.) per gram of dry air

Mixing ratio of refrigerant composition/air: 1 vol. % increments±0.2vol. %

Mixture of refrigerant composition: ±0.1 mass %

Ignition method: AC discharge, voltage: 15 kV, electric current: 30 mA,neon transformer

Electrode spacing: 6.4 mm (¼ inch)

Spark: 0.4 seconds±0.05 seconds

Evaluation Criteria:

When the flame spread at an angle of more than 90° from the ignitionpoint, it was evaluated that flame propagation was present (flammable).

When the flame spread at an angle of 90° or less from the ignitionpoint, it was evaluated that flame propagation was absent(non-flammable).

TABLE 12 Comparative Comparative Example Example Example Example ExampleExample Item Unit 4-1 4-2 4-1 4-2 4-3 4-4 Composition HFO-1132 (E) mass% 0 15.0 21.0 23.6 24.3 25.1 ratio HFO-1234yf mass % 100.0 85.0 79.076.4 75.7 74.9 GWP (AR4) — 4 5 5 5 5 6 Discharge temperature ° C. 54.461.3 63.1 63.8 64.0 64.2 Saturation pressure MPa 0.222 0.350 0.383 0.3960.400 0.403 (−10° C.) Critical temperature ° C. 94.7 88.1 85.9 85.0 84.884.5 COP ratio (relative to % 100.0 99.1 98.8 98.6 98.5 98.4 R1234yf)Refrigerating capacity % 100.0 129.8 140.0 144.2 145.4 146.6 ratio(relative to R1234yf) ASHRAE flammability — Class 2L Class 2L Class 2LClass 2L Class 2L Class 2L classification Comparative ComparativeComparative Example Example Example Example Example Example Item 4-5 4-64-7 4-3 4-4 4-5 Composition HFO-1132 (E) 26.7 27.5 28.4 30.0 40.0 50.0ratio HFO-1234yf 73.3 72.5 71.6 70.0 60.0 50.0 GWP (AR4) 6 6 6 6 6 7Discharge temperature 64.6 64.8 65.0 65.4 67.5 69.4 Saturation pressure0.411 0.414 0.418 0.425 0.461 0.492 (−10° C.) Critical temperature 84.083.8 83.5 83.0 80.5 78.7 COP ratio (relative to 98.3 98.2 98.2 98.0 97.296.6 R1234yf) Refrigerating capacity 149.1 150.3 151.7 154.1 168.2 181.3ratio (relative to R1234yf) ASHRAE flammability Class 2L Class 2L Class2L Class 2L Class 2L Class 2L classification

Test Example 5

The GWP of each mixed refrigerant shown in Examples 5-1 to 5-13,Comparative Examples 5-1 to 5-3, and Reference Example 5-1 (R134a) wasevaluated based on the values in the IPCC fourth report.

The COP, refrigerating capacity, boiling point, and dischargetemperature of each of the mixed refrigerants were determined byperforming refrigeration cycle theoretical calculations for the mixedrefrigerants using the National Institute of Science and Technology(NIST) and Reference Fluid Thermodynamic and Transport PropertiesDatabase (Refprop 10.0) under the following conditions.

Evaporation temperature: −30° C.

Condensation temperature: 30° C.

Superheating temperature: 5 K

Supercooling temperature: 5 K

Compressor efficiency: 70%

The “evaporation temperature of −30° C.” means that the evaporationtemperature of the mixed refrigerant in the evaporator provided in therefrigeration apparatus is −30° C. Further, the “condensationtemperature of 30° C.” means that the condensation temperature of themixed refrigerant in the condenser provided in the refrigerationapparatus is 30° C.

Table 13 shows the results of Test Example 5. Table 13 shows Examplesand Comparative Examples with regard to a refrigerant 5 of the presentdisclosure. In Table 13, the “COP ratio” and the “refrigerating capacityratio” refer to a ratio (%) relative to R1234yf. In Table 13, the“discharge temperature (° C.)” refers to a temperature at which therefrigerant has the highest temperature in the refrigeration cycletheoretical calculations of the mixed refrigerant. In Table 13, the“boiling point (° C.)” means a temperature at which the liquid phase ofthe mixed refrigerant has atmospheric pressure (101.33 kPa). In Table13, the “motor power consumption amount (%)” refers to electrical energyused to enable an electric car to run, and is expressed as a ratio withrespect to a power consumption amount when the refrigerant isHFO-1234yf. In Table 13, the “heater power consumption amount (%)”refers to electrical energy used to enable a heater to be driven, and isexpressed as a ratio with respect to a power consumption amount when therefrigerant is HFO-1234yf. In Table 13, the “drivable distance” refersto a distance drivable by an electric car equipped with a rechargeablebattery having a constant electric capacity while having a heater turnedon, and is expressed as a ratio (%) relative to a drivable distance(100%) when the car is driven without a heater turned on (i.e., heaterpower consumption is 0).

The coefficient of performance (COP) was calculated according to thefollowing equation.COP=(refrigerating capacity or heating capacity)/amount of electricalpower consumed

The flammability of the mixed refrigerant was determined by specifyingthe fractionation of the mixed refrigerant to the WCF concentration andmeasuring the burning rate according to ANSI/ASHRAE Standard 34-2013.The burning rate was measured as follows. First, a mixed refrigeranthaving a purity of 99.5% or more was used, and the mixed refrigerant wasdeaerated by repeating a cycle of freezing, pumping, and thawing untilno trace of air was observed on the vacuum gauge. The burning rate wasmeasured by a closed method. The initial temperature was the ambienttemperature. The ignition was performed by generating an electricalspark between the electrodes in the center of the sample cell. Theduration of the discharge was 1.0 to 9.9 ms, and the ignition energy wastypically about 0.1 to 1.0 J. The spread of the flame was visualized byusing a schlieren photograph. A cylindrical container (inner diameter:155 mm, length: 198 mm) having two acrylic windows that transmit lightwas used as a sample cell, and a xenon lamp was used as a light source.The schlieren image of the flame was recorded using a high-speed digitalvideo camera at a frame speed of 600 fps, and stored in a PC.

Heating was performed by using an electrical heater in the case of arefrigerant having a boiling point of more than −40° C., and using aheat pump in the case of a refrigerant having a boiling point of −40° C.or less.

The power consumption amount when the heater was used was calculatedaccording to the following equation.Power consumption amount when the heater was used=heating capacity/COPof heater

The COP of the heater refers to heating efficiency.

With regard to the heating efficiency, the COP of the heater is 1 in anelectric heater, and the heater consumes an electrode equivalent to themotor power. That is, the power consumption of the heater isE=E/(1+COP). In the case of a heat pump, the COP of the heater wasdetermined by performing refrigeration cycle theoretical calculationsfor the mixed refrigerants using the National Institute of Science andTechnology (NIST) and Reference Fluid Thermodynamic and TransportProperties Database (Refprop 10.0) under the following conditions.

Evaporation temperature: −30° C.

Condensation temperature: 30° C.

Superheating temperature: 5 K

Supercooling temperature: 5 K

Compressor efficiency: 70%

The drivable distance was calculated according to the followingequation.Drivable distance=(battery capacity)/(motor power consumptionamount+heater power consumption amount)

TABLE 13 Reference Comp. Comp. Example Example Example Example ExampleExample Item Unit Example 5-1 Ex. 5-1 Ex. 5-2 5-1 5-2 5-3 5-4 5-5 5-6Composition HFO-1132 (E) mass % 0.0 0 10.0 12.1 15.0 20.0 25.0 30.0 35.0ratio HFO-1234yf mass % 0.0 100.0 90.0 87.9 85.0 80.0 75.0 70.0 65.0HFC-134a mass % 100.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 GWP (AR4) — 1430 45 5 5 5 6 6 6 COP ratio (relative to % 105 100 100 100 100 100 100 100100 R1234yf) Refrigerating capacity % 99 100 123 128 134 145 155 165 175ratio (relative to 1234yf) Motor power % 100 100 100 100 100 100 100 100100 consumption amount Heater power % 95 100 100 33 33 33 33 33 33consumption amount Drivable distance % 100 100 100 100 100 100 100 100100 (without heater) Drivable distance % 50 50 50 84 84 84 84 84 84(with heater) Discharge temperature ° C. 66.0 48.0 54.8 56.0 57.5 59.861.9 63.9 65.8 Combustion rate cm/s 0.0 1.5 1.5 1.5 1.5 1.5 1.5 1.5 2.0Boiling point ° C. −26.1 −29.5 −38.8 −40.0 −41.4 −43.3 −44.7 −45.9 −46.9Saturation pressure kPaG −50.1 −39 −4.4 0.9 7.5 17.2 25.3 32.3 38.4 at−40° C. Heating method System Electric Electric Electric Heat Heat HeatHeat Heat Heat heater heater heater pump pump pump pump pump pumpExample Example Example Example Example Example Example Comp. Item 5-75-8 5-9 5-10 5-11 5-12 5-13 Ex. 5-3 Composition HFO-1132 (E) 40.0 45.050.0 55.0 60.0 65.0 72.0 75.0 ratio HFO-1234yf 60.0 55.0 50.0 45.0 40.035.0 28.0 25.0 HFC-134a 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 GWP (AR4) 6 7 77 8 8 8 9 COP ratio (relative to 100 100 100 100 100 100 100 100R1234yf) Refrigerating capacity 185 194 203 212 220 229 240 245 ratio(relative to 1234yf) Motor power 100 100 100 100 100 100 100 100consumption amount Heater power 33 33 33 33 33 33 33 33 consumptionamount Drivable distance 100 100 100 100 100 100 100 100 (withoutheater) Drivable distance 84 84 84 84 84 84 84 84 (with heater)Discharge temperature 67.6 69.3 70.9 72.6 74.2 75.9 78.2 79.2 Combustionrate 2.6 3.4 4.3 5.3 6.5 7.8 9.9 10.9 Boiling point −47.7 −48.4 −49.1−49.6 −50.2 −50.5 −51.2 −51.4 Saturation pressure 43.9 48.8 53.4 57.561.4 65.0 69.6 71.5 at −40° C. Heating method Heat Heat Heat Heat HeatHeat Heat Heat pump pump pump pump pump pump pump pump

REFERENCE NUMERALS

-   1: Supply Line-   2: Sampling Line-   3: Thermometer-   4: Pressure Gauge-   5: Electrode-   6: Stirring Blade (produced by PTFE)

The invention claimed is:
 1. A refrigeration method comprising operatinga refrigeration cycle, in which the evaporation temperature is −75 to−5° C., using a composition comprising a refrigerant, the refrigerantcomprising trans-1,2-difluoroethylene (HFO-1132 (E)) and2,3,3,3-tetrafluoropropene (HFO-1234yf), wherein the refrigerantcomprises HFO-1132 (E) and HFO-1234yf in such amounts that the sum ofHFO-1132 (E) and HFO-1234yf is 99.5 mass % or more, wherein HFO-1132 (E)is present in an amount of 35.0 to 65.0 mass %, and HFO-1234yf ispresent in an amount of 65.0 to 35.0 mass %, based on the total mass ofHFO-1132 (E) and HFO-1234yf.
 2. The refrigeration method according toclaim 1, wherein the refrigerant is an alternative refrigerant forR407C, R452B, R454B, or R454C.
 3. The refrigeration method according toclaim 1, wherein the method comprises operating equipment designed forR407C, R452B, R454B, or R454C with the refrigerant comprising HFO-1132(E) and HFO-1234yf.
 4. The refrigeration method according to claim 1,wherein the refrigerant further comprises an additional refrigerant,wherein the additional refrigerant is present in an amount of 0.5 mass %or less, based on the total amount of HFO-1132 (E), HFO-1234yf, and theadditional refrigerant taken as 100 mass %.
 5. A composition comprisinga refrigerant, the refrigerant comprising trans-1,2-difluoroethylene(HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), wherein therefrigerant comprises HFO-1132 (E) and HFO-1234yf in such amounts thatthe sum of HFO-1132 (E) and HFO-1234yf is 99.5 mass % or more, whereinHFO-1132 (E) is present in an amount of 31.1 to 39.8 mass %, andHFO-1234yf is present in an amount of 68.9 to 60.2 mass %, based on thetotal mass of HFO-1132 (E) and HFO-1234yf.
 6. The composition accordingto claim 5, wherein HFO-1132 (E) is present in an amount of 31.1 to 37.9mass %, and HFO-1234yf is present in an amount of 68.9 to 62.1 mass %,based on the total mass of HFO-1132 (E) and HFO-1234yf.
 7. Thecomposition according to claim 5, wherein the refrigerant furthercomprises an additional refrigerant, wherein the additional refrigerantis present in an amount of 0.5 mass % or less, based on the total amountof HFO-1132 (E), HFO-1234yf, and the additional refrigerant taken as 100mass %.
 8. The composition according to claim 6, wherein the refrigerantfurther comprises an additional refrigerant, wherein the additionalrefrigerant is present in an amount of 0.5 mass % or less, based on thetotal amount of HFO-1132 (E), HFO-1234yf, and the additional refrigeranttaken as 100 mass %.
 9. A composition comprising a refrigerant, therefrigerant comprising trans-1,2-difluoroethylene (HFO-1132 (E)) and2,3,3,3-tetrafluoropropene (HFO-1234yf), wherein the refrigerantcomprises HFO-1132 (E) and HFO-1234yf in such amounts that the sum ofHFO-1132 (E) and HFO-1234yf is 99.5 mass % or more, wherein HFO-1132 (E)is present in an amount of 21.0 to 28.4 mass %, and HFO-1234yf ispresent in an amount of 79.0 to 71.6 mass %, based on the total mass ofHFO-1132 (E) and HFO-1234yf.
 10. The composition according to claim 9,wherein the refrigerant further comprises an additional refrigerant,wherein the additional refrigerant is present in an amount of 0.5 mass %or less, based on the total amount of HFO-1132 (E), HFO-1234yf, and theadditional refrigerant taken as 100 mass %.
 11. A composition comprisinga refrigerant, the refrigerant comprising trans-1,2-difluoroethylene(HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), wherein therefrigerant comprises HFO-1132 (E) and HFO-1234yf in such amounts thatthe sum of HFO-1132 (E) and HFO-1234yf is 99.7 mass % or more, whereinHFO-1132 (E) is present in an amount of 12.1 to 45.0 mass %, andHFO-1234yf is present in an amount of 55.0 to 28.0 mass %, based on thetotal mass of HFO-1132 (E) and HFO-1234yf.
 12. The composition accordingto claim 11, wherein the refrigerant further comprises an additionalrefrigerant, wherein the additional refrigerant is present in an amountof 0.3 mass % or less, based on the total amount of HFO-1132 (E),HFO-1234yf, and the additional refrigerant taken as 100 mass %.